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1.
Chemosphere ; 355: 141775, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38522676

RESUMO

The catalyst's composition and rationally designed structure is significantly interlinked with its performance for wastewater remediation. Here, a novel hollow cobalt phosphides/carbon (HCoP/C) as an efficient catalyst for activating peroxymonosulfate (PMS) was prepared. The ZIF-67 was synthesized first, followed by phytic acid (PA) etching and then heat treatment was used to get HCoP/C. The PA was used as an etching agent and a source of phosphorus to prepare HCoP/C. To analyze catalytic performance, another solid cobalt phosphides/carbon (SCoP/C) catalyst was prepared for comparison. In contrast to SCoP/C, the HCoP/C exhibited higher catalytic efficiency when used to activate PMS to degrade Bisphenol A (BPA). The results showed that about 98 % of targeted pollutant BPA was removed from the system in 6 min with a rate constant of 0.78 min-1, which was 4 times higher than the solid structure catalyst. The higher catalytic performance of HCoP/C is attributed to its hollow structure. In the study, other parameters such as BPA concentration, temperature, pH, and different catalyst amount were also tested. Moreover, the electron paramagnetic resonance (EPR) and radical quenching analysis confirmed that sulfate radicals were dominant in the HCoP/C/PMS system.


Assuntos
Compostos Benzidrílicos , Carbono , Estruturas Metalorgânicas , Fenóis , Carbono/química , Ácido Fítico , Peróxidos/química , Cobalto/química
2.
Int J Biol Macromol ; 265(Pt 2): 130519, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38553393

RESUMO

Peroxymonosulfate (PMS), which is dominated by non-free radical pathway, has a good removal effect on organic pollutants in complex water matrices. In this article, a biodegradable cobalt-based catalyst (Co3O4/MoS2@NCS) was synthesized by a simple hydrothermal method with chitosan (CS) as nitrogen­carbon precursor and doped with Cobaltic­cobaltous oxide (Co3O4) and Molybdenum disulfide (MoS2), and was used to activate PMS to degrade dye wastewater. Electrochemical tests showed that Co3O4/MoS2@NCS exhibited higher current density and cycling area than MoS2@NCS and MoS2. In the Co3O4/MoS2@NCS/PMS system, the degradation rate of 30 mg·L-1 rhodamine B (RhB) reached 97.75 % within 5 min, and kept as high as 94.34 % after 5 cycles. Its rate constant was 1.91 and 8.37 times that of MoS2@NCS/PMS and MoS2/PMS, respectively. It had good complex background matrices and acid-base anti-interference ability, and had good universality and reusability. The degradation rate of methyl orange (MO) and methylene blue (MB) were more than 91 % within 5 min at pH 4.8. The experimental results demonstrated that MoS2-modified CS as a carrier exposed a large number of active sites, which not only dispersed Co3O4 nanoparticles and improved the stability of the catalyst, but also provided abundant electron rich groups, and promoted the activation of PMS and the production of reactive oxygen species (ROS). PMS was effectively activated by catalytic sites (Co3+/Co2+, Mo4+/Mo5+/Mo6+, CO, pyridine N, pyrrole N, hydroxyl group and unsaturated sulfur), producing a large number of radicals that attack RhB molecules, causing chromophore cleavage, ring opening, and mineralization. Among them, non-free radical 1O2 was the main ROS for RhB degradation. This work is expected to provide a new idea for the design and synthesis of environmentally friendly and efficient MoS2-modified cobalt-based catalysts.


Assuntos
Carbono , Quitosana , Óxidos , Peróxidos , Carbono/química , Espécies Reativas de Oxigênio/química , Molibdênio/química , Cobalto/química
3.
J Colloid Interface Sci ; 663: 909-918, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38447405

RESUMO

Peroxymonosulfate (PMS) is widely employed to generate oxygen-containing reactive species for ciprofloxacin (CIP) degradation. Herein, cobalt oxyhydroxide @activated carbon (CoOOH@AC) was synthesized via a wet chemical sedimentation method to activate PMS for degradation of CIP. The result suggested AC can support the vertical growth of CoOOH nanosheets to expose high-activity Co-contained edges, possessing efficient PMS activation and degradation activity and catalytic stability. In the presence of 3.0 mg of optimal CoOOH@AC and 2 mM PMS, 96.8 % of CIP was degraded within 10 min, approximately 11.6 and 9.97 times greater than those of CoOOH/PMS and AC/PMS systems. Notably, it was disclosed that the optimal CoOOH@AC/PMS system still exhibited efficient catalytic performance in a wide pH range, different organics and common co-existing ions. Quenching experiments and electron paramagnetic resonance indicated that both radical and non-radical processes contributed to the degradation of CIP, with 1O2 and direct electron transfer accounting for the non-radical pathway and SO4•- and •OH serving as the main radical active species. Finally, possible CIP degradation pathways were proposed based on high-performance liquid chromatography-mass spectrometry. This study provided an alternate method for wastewater treatment based on PMS catalyzed by cobalt-based hydroxide.


Assuntos
Carvão Vegetal , Ciprofloxacina , Hidróxidos , Óxidos , Ciprofloxacina/química , Peróxidos/química , Cobalto/química , Espécies Reativas de Oxigênio
4.
Environ Sci Technol ; 58(14): 6444-6454, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38551318

RESUMO

Catalyst design with a "Co-N-C" structure at the atomic level has shown great interest for peroxymonosulfate (PMS) activation toward advanced oxidation water treatment. Here, we present an innovative way of producing cobalt hexacyanocobaltate (Co-HCC) with an abundance of atomically isolated CoII-NC sites at the outer surface. This material allows ultraefficient PMS activation to generate plenty of sulfate and hydroxyl radicals, with a turnover frequency much higher than those of most cobalt-based catalysts reported so far and even the homogeneous catalysis by Co2+ ions. We gained fundamental insights on its unprecedently high catalytic performance based on experimental results and computational study. Then, we controlled the growth of Co-HCC on a ceramic membrane to form a confined oxidation environment that utilizes the extended surface area and maximal exposure of short-lived radicals for a fast removal of organic pollutants that enter the pores. As a result, this catalytic membrane achieves complete disruption of micropollutants under a water flux up to 10,000 LMH (merely 0.2 s retention time) and further >90% mineralization of organic pollutants in complex industrial wastewater matrices (<100 s retention time), together with the merits of operational simplicity and great longevity (2 weeks continuous run). Our study elicits a new milestone in "Co-N-C" catalyst structure design for PMS activation and highlights the great interest of producing catalytic membranes for a confined treatment of organic pollutants from partial oxidation to complete mineralization as a new benchmark.


Assuntos
Carcinoma Hepatocelular , Poluentes Ambientais , Neoplasias Hepáticas , Humanos , Cobalto/química , Cianetos , Peróxidos/química , Catálise
5.
Dalton Trans ; 53(14): 6311-6322, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38487871

RESUMO

While platinum(II)-based drugs continue to be employed in cancer treatments, the escalating occurrence of severe side effects has spurred researchers to explore novel sources for potential therapeutic agents. Notably, cobalt(III) has emerged as a subject of considerable interest due to its ubiquitous role in human physiology. Several studies investigating the anticancer effects of Salphen complexes derived from cobalt(III) have unveiled intriguing antiproliferative properties. In a bid to enhance our understanding of this class of compounds, we synthesized and characterized two novel half Salphen cobalt(III) complexes. Both compounds exhibited notable stability, even in the presence of physiologically relevant concentrations of glutathione. The application of spectroscopic and computational methodologies unravelled their interactions with duplex and G4-DNAs, suggesting an external binding affinity for these structures, with preliminary indications of selectivity trends. Importantly, antiproliferative assays conducted on 3D cultured SW-1353 cancer cells unveiled a compelling anticancer activity at low micromolar concentrations, underscoring the potential therapeutic efficacy of this novel class of cobalt(III) complexes.


Assuntos
Antineoplásicos , Complexos de Coordenação , Humanos , Complexos de Coordenação/química , Cobalto/farmacologia , Cobalto/química , Fenilenodiaminas/química , DNA/química , Antineoplásicos/química
6.
Anal Methods ; 16(14): 2044-2050, 2024 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-38501322

RESUMO

The preparation of cobalt-based nanozymes with high oxidase-like activity still needs more efforts. In this paper, we report the synthesis of a CoO/Co-tryptophan-functional graphene quantum dot hybrid (CoO/Co-Try-GQD). Firstly, cobalt ions coordinate with the indole nitrogen on Try-GQD to form a complex, followed by thermal reduction and oxidation. The resulting hybrid presents a three-dimensional network structure, and CoO/Co nanoparticles are uniformly dispersed on the graphene sheet with an average size of 10 ± 0.24 nm. This unique structure improved the oxidase-like activity of the hybrid, enabling it to catalyze the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to rapidly produce deep blue ox-TMB with a strong absorbance at 652 nm (A652). A colorimetric method was developed for the highly sensitive determination of L-cysteine (L-cys) based on the inhibition of the hybrid's oxidase-like activity and low A652 caused by the binding of L-cys with Co atoms on CoO/Co via the Co-S bond. The A652 linearly decreased with increasing L-cys concentration in the range of 0.05-2 µM, and the detection limit was 0.032 µM. Further, the established method has been successfully applied to the determination of L-cys in milk.


Assuntos
Benzidinas , Grafite , Pontos Quânticos , Grafite/química , Cisteína/metabolismo , Pontos Quânticos/química , Colorimetria/métodos , Oxirredutases/química , Oxirredutases/metabolismo , Cobalto/química , Estresse Oxidativo
7.
ACS Appl Mater Interfaces ; 16(13): 15959-15969, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38511635

RESUMO

Perfluorooctanesulfonate (PFOS), an emerging organic contaminant, necessitates robust on-site detection strategies to safeguard human health and ecological balance. This study introduces a novel point-of-care testing (POCT) platform, combining a hydrogel kit with nanozymes and smartphone technology, for the highly sensitive detection of PFOS. The strategy utilizes copper-substituted cobalt-based Prussian blue analogue nanoboxes (CuCo-PBA NBs), which exhibit intricate hollow structures and remarkable peroxidase-like catalytic activity, efficiently catalyzing the oxidation of chromogenic substrates with hydrogen peroxide (H2O2). Density functional theory calculations elucidate the adsorption dynamics of H2O2 on CuCo-PBA NBs, identifying the factors that improve the catalytic efficiency. The colorimetric POCT platform, integrating the hydrogel kit with a smartphone interface, demonstrates practical utility and achieves a detection limit of 1.43 × 10-8 mol L-1 for PFOS. This research not only presents a new nanozyme design for PFOS detection in diverse matrices, such as lake water, whole blood, urine, and milk, but also paves the way for developing a portable and efficient POCT platform for a variety of emerging contaminants.


Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Hidrogéis , Peróxido de Hidrogênio , Humanos , Oxirredutases , Peroxidase/química , Peroxidases , Cobalto/química , Colorimetria
8.
Mikrochim Acta ; 191(4): 200, 2024 03 15.
Artigo em Inglês | MEDLINE | ID: mdl-38488888

RESUMO

A single-holed cobalt - nitrogen - carbon (Co - N - C) hollow structure nanozyme has been fabricated by in situ growth of zeolitic imidazolate framework (ZIF - 67) on the polystyrene (PS) sphere and following treatment by high-temperature carbonization. The Co - N - C nanostructure mimics the activity of oxidase and can activate O2 into reactive oxygen species (ROS), giving a remarkable enhancement on the chemiluminescence (CL) signal of luminol - O2 reaction. The Co - N - C oxidase mimic has further been exploited in the biosensing field by the determination of the activity of ß - galactosidase (ß - gal). The CL method for ß - gal activity has a linear range of 0.5 mU·L-1 to 5.0 U·L-1, a detection limit of 0.167 mU·L-1, and the precision of 3.1% (5.0 U·L-1, n = 11). This method has been employed to assess inhibitor screening of ß - gal and determine activity of ß - gal in spiked human serum samples.


Assuntos
Carbono , Oxirredutases , Humanos , Oxirredutases/química , Carbono/química , Cobalto/química , Nitrogênio , Luminescência , Galactosidases
9.
Chemosphere ; 352: 141346, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38311035

RESUMO

Doping proves to be an efficacious method of establishing intermetallic interactions for enhancing toluene oxidation performance of bimetallic oxides. However, conventional bimetallic oxide catalysts are yet to overcome their inadequacy in establishing intermetallic interactions. In this work, the dispersion of Mn-Co bimetallic sites was improved by hydrolytic co-precipitation, strengthening the intermetallic interactions which improved the structural and physicochemical properties of the catalysts, thus significantly enhancing its catalytic behavior. MnCo-H catalysts fabricated by the hydrolytic co-precipitation method showed promising catalytic performance (T50 = 223 °C, T90 = 229 °C), robust stability (at least 100 h) and impressive water resistance (under 10 vol.% of water) for toluene elimination. Hydrolytic co-precipitation has been found to improve dispersion of MnCo elements and to enhance interaction between Co and Mn ions (Mn4+ + Co2+ = Mn3+ + Co3+), resulting in a lower reduction temperature (215 °C) and a weaker Mn-O bond strength, creating more lattice defects and oxygen vacancies, which are responsible for superior catalytic properties of MnCo-H samples. Furthermore, in situ DRIFTs showed that gaseous toluene molecules adsorbed on the surface of MnCo-H were continuously oxidized to benzyl alcohol → benzaldehyde → benzoate, followed by a ring-opening reaction with surface-activated oxygen to convert to maleic anhydride as the final intermediate, which further generates water and carbon dioxide. It was also revealed that the ring-opening reaction for the conversion of benzoic acid to maleic anhydride is the rate-controlling step. This study reveals that optimizing active sites and improving reactive oxygen species by altering the dispersion of bimetals to enhance bimetallic interactions is an effective strategy for the improvement of catalytic behavior, while the hydrolytic co-precipitation method fits well with this corollary.


Assuntos
Compostos de Manganês , Manganês , Compostos de Nitrosoureia , Tolueno , Manganês/química , Oxirredução , Tolueno/química , Anidridos Maleicos , Óxidos/química , Água , Cobalto/química , Oxigênio/química , Catálise
10.
Analyst ; 149(5): 1455-1463, 2024 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-38190248

RESUMO

In this work, we prepared a simple and low-cost cobalt-doped Prussian blue analog (Co-PBA), which can directly oxidize 10-acetyl-3,7-dihydroxyphenoxazine and 3,3',5,5'-tetramethylbenzidine (TMB) to produce resorufin (ox-AR) with high fluorescent quantum yield and ox-TMB with blue color, respectively, without the need for unstable H2O2. Using the Michaelis-Menten curve and Lineweaver-Burk equation, the Michaelis-Menten constant of Co-PBA and the substrate TMB was found to be 0.033 mM, which was much lower than horseradish peroxidase and other reported nanozymes, showing satisfactory substrate affinity. Uric acid (UA) can cause erosion of the Co-PBA structure, and it significantly reduces the catalytic activity of Co-PBA, resulting in the decrease of the fluorescence emission signal of ox-AR and the absorption signal of ox-TMB. Based on this, a simple, sensitive, and fast fluorescence/colorimetric dual-mode uric acid detection platform was established. The detection range for UA by fluorescence method is 0.625-40 µM, and the detection limit (LOD, S/N = 3) is as low as 0.389 µM. The detection system was applied to serum samples with good recovery and can be used for field detection of UA in biological samples under different environments to meet different needs.


Assuntos
Ferrocianetos , Oxirredutases , Ácido Úrico , Colorimetria/métodos , Cobalto/química , Peróxido de Hidrogênio/química
11.
Angew Chem Int Ed Engl ; 63(13): e202317419, 2024 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-38251394

RESUMO

A typical component of polymer waste is polystyrene (PS) used in numerous applications, but degraded only slowly in the environment due to its hydrophobic properties. To increase the reactivity of polystyrene, polar groups need to be introduced. Here, biohybrid catalysts based on the engineered anchor peptide LCI_F16C are presented, which are capable of attaching to polystyrene microparticles and hydroxylating benzylic C-H bonds in polystyrene microparticles using commercially available oxone as oxidant. LCI peptides achieve a dense surface coverage of PS through monolayer formation within minutes in aqueous solutions at ambient temperature. The catalytically active cobalt cofactor Co-L1 or Co-L2 with a modified NNNN macrocyclic TACD ligand (TACD=1,4,7,10-tetraazacyclododecane) is covalently bound to the anchor peptide LCI through a maleimide linker. Compared to the free cofactors, a 12- to 15-fold improvement in catalytic activity using biohybrid catalysts based on LCI_F16C was observed.


Assuntos
Cobalto , Poliestirenos , Cobalto/química , Poliestirenos/química , Oxirredução , Polímeros/química , Peptídeos/química
12.
J Pharmacol Exp Ther ; 388(2): 596-604, 2024 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-38182416

RESUMO

There do not appear to be any established therapeutics for treating azide poisoning at this time, and presently available antidotes to cyanide poisoning are far from ideal, being particularly impractical for use if multiple victims present. The cobalt (II/III) complex of the Schiff-base ligand trans-[14]-diene (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene (CoN4[14]) is shown to act as an effective antidote to both azide and cyanide toxicity in mice. Groups of animals challenged with an LD40 dose of NaCN (100 µmol/kg i.p.) exhibited significantly faster recovery from knockdown and fewer (zero) deaths if given CoN4[14] (50 µmol/kg i.p.) 2 minutes after the toxicant. Groups of animals challenged with an essentially lethal dose of NaCN (1.5 x LD50 = 150 µmol/kg i.p.) all survived if given the CoN4[14] (75 µmol/kg i.p.) 5 minutes before the toxicant dose. These data represent improved antidotal capability over the Food and Drug Administration-approved cobalt-based cyanide antidote hydroxocobalamin. Recovery of animals challenged sublethally with NaN3 (415 µmol/kg i.p.) was assessed employing a modified pole-climbing test. Mice given the CoN4[14] antidote (70 µg/kg i.p.) 5 minutes after the toxicant dose recovered twice as fast as the controls given no antidote. The interactions of cyanide and azide with CoN4[14] in vitro (buffered aqueous solutions) have been further investigated by a combination of spectroscopic approaches. The Co(II) form of the complex is able to bind two CN- anions while only binding a single N3 -, providing a reasonable explanation for the difference between their therapeutic abilities. SIGNIFICANCE STATEMENT: The Schiff-base complex CoN4[14] is shown to be an effective antidote to cyanide in mice, with improved therapeutic capabilities compared to the Food and Drug Administration-approved cobalt-containing hydroxocobalamin. CoN4[14] is also antidotal in mice toward azide poisoning, for which there is seemingly no approved therapy currently available. The activity toward cyanide involves a "redox-switching" mechanism that could be a common, but largely unrecognized, feature of all cobalt-based cyanide antidotes in use and under development.


Assuntos
Antídotos , Hidroxocobalamina , Estados Unidos , Animais , Camundongos , Antídotos/farmacologia , Antídotos/uso terapêutico , Hidroxocobalamina/farmacologia , Hidroxocobalamina/uso terapêutico , Azidas , Cobalto/química , Cianetos/química , Bases de Schiff/química
13.
Environ Sci Technol ; 58(4): 2153-2161, 2024 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-38244211

RESUMO

Nitrous oxide (N2O) has a detrimental impact on the greenhouse effect, and its efficient catalytic decomposition at low temperatures remains challenging. Herein, the cobalt-based high-entropy oxide with a spinel-type structure (Co-HEO) is successfully fabricated via a facile coprecipitation method for N2O catalytic decomposition. The obtained Co-HEO catalyst displays more remarkable catalytic performance and higher thermal stability compared with single and binary Co-based oxides, as the temperature of 90% N2O decomposition (T90) is 356 °C. A series of characterization results reveal that the synergistic effect of multiple elements enhances the reducibility and augments oxygen vacancy in the high-entropy system, thus boosting the activity of the Co-HEO catalyst. Moreover, density functional theory (DFT) calculations and the temperature-programmed surface reaction (TPSR) with isotope labeling demonstrate that N2O decomposition on the Co-HEO catalyst follows the Langmuir-Hinshelwood (L-H) mechanism with the promotion of abundant oxygen vacancies. This work provides a fundamental understanding of the synergistic catalytic effect in N2O decomposition and paves the way for the novel environmental catalytic applications of HEO.


Assuntos
Cobalto , Óxidos , Entropia , Óxidos/química , Cobalto/química , Oxigênio
14.
Chemosphere ; 350: 141098, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38171398

RESUMO

To fulfill the unprecedented valorization approaches for lignocellulose, this work focuses on the potential of lignin-derived catalytic systems for bio-remediation, which are natural materials perceived to address the increased demand for eco-conscious catalyzed processes. A useful lignin-functionalized cobalt (Lig-Co) catalyst has been prepared, well-characterized and deployed for the catalyzed reducing decomposition of stable harmful organic pollutants such as methylene blue (MB) and methyl orange (MO), in simple and binary systems. The multifunctional character of lignin and the presence of various active sites can promote effectively loaded metal nanoparticles (NPs). Considerably, optimizing detoxification tests showed that the uncatalyzed use of NaBH4 as a reductive agent led to an incomplete reduction of organic contaminants over a long period of up to 65 min. Interestingly, Lig-Co catalyst exhibited a high reduction rate and turnover frequency of up to 99.23% and 24.12 min-1 for MB, respectively, while they reached 99.25% and 26.21 min-1 for MO at normal temperature. Kinetically quick catalytic reaction was also demonstrated for the hybrid system, in which the rate constant k was 0.175 s-1 and 0.165 s-1 for MB and MO, respectively, within a distinctly low reaction time of around 120 s. The reproducibility of the Lig-Co catalyst induces a desirable capacity to reduce stable dyes present simultaneously in the binary system, with 6 successive catalytic runs and over 80% of activity retained. Such robust findings underline the considerable interest in developing future lignin-mediated catalytic transformations and upscaling biomass-derived products, to meet the growing demand for sustainable and eco-friendly alternatives in various industries.


Assuntos
Compostos Azo , Cobalto , Lignina , Lignina/química , Cobalto/química , Reprodutibilidade dos Testes , Corantes/química , Catálise
15.
Acta Biomater ; 176: 445-457, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38190928

RESUMO

The incorporation of cobalt ions into the composition of bioactive glasses has emerged as a strategy of interest for bone regeneration purposes. In the present work, we have designed a set of bioactive mesoporous glasses SiO2-CaO-P2O5-CoO (Co-MBGs) with different amounts of cobalt. The physicochemical changes introduced by the Co2+ ion, the in vitro effects of Co-MBGs on preosteoblasts and endothelial cells and their in vivo behaviour using them as bone grafts in a sheep model were studied. The results show that Co2+ ions neither destroy mesoporous ordering nor inhibit in vitro bioactive behaviour, exerting a dual role as network former and modifier for CoO concentrations above 3 % mol. On the other hand, the activity of Co-MBGs on MC3T3-E1 preosteoblasts and HUVEC vascular endothelial cells is dependent on the concentration of CoO present in the glass. For low Co-MBGs concentrations (1mg/ml) cell viability is not affected, while the expression of osteogenic (ALP, RUNX2 and OC) and angiogenic (VEGF) genes is stimulated. For Co-MBGs concentration of 5 mg/ml, cell viability decreases as a function of the CoO content. In vivo studies show that the incorporation of Co2+ ions to the MBGs improves the bone regeneration activity of these materials, despite the deleterious effect that this ion has on bone-forming cells for any of the Co-MBG compositions studied. This contradictory effect is explained by the marked increase in angiogenesis that takes place inside the bone defect, leading to an angiogenesis-osteogenesis coupling that compensates for the partial decrease in osteoblast cells. STATEMENT OF SIGNIFICANCE: The development of new bone grafts implies to address the need for osteogenesis-angiogenesis coupling that allows bone regeneration with viable tissue in the long term. In this sense the incorporation of cobalt ions into the composition of bioactive glasses has emerged as a strategy of great interest in this field. Due to the potential cytotoxic effect of cobalt ions, there is an important controversy regarding the suitability of their incorporation in bone grafts. In this work, we address this controversy after the implantation of cobalt-doped mesoporous bioactive glasses in a sheep model. The incorporation of cobalt ions in bioactive glasses improves the bone regeneration ability of these bone grafts, due to enhancement of the angiogenesis-osteogenesis coupling.


Assuntos
Células Endoteliais , Osteogênese , Animais , Ovinos , Cobalto/farmacologia , Cobalto/química , Dióxido de Silício , Íons , Vidro/química
16.
Chemosphere ; 351: 141207, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38266877

RESUMO

In this study, a vitamin C-regulated CoAl-layered double hydroxide with abundant oxygen vacancies was synthesized via a simple hydrothermal process. The resulting CoAl-layered double hydroxide was employed to activate peroxydisulfate for removal of sulfamethoxazole. The effect of the experimental parameters such as pH, catalyst dose and peroxydisulfate concentration on sulfamethoxazole removal was investigated. The current system exhibited excellent catalytic performance for sulfamethoxazole removal in a broad pH range (i.e., pH 3.0-11.0). Under the optimized condition, 94.2% of sulfamethoxazole was degraded within 15 min, accompanied by a 67.6% reduction in chemical oxygen demand. The effective sulfamethoxazole degradation could be attributed to four pathways. Firstly, the ≡ Co2+ in catalyst reacted with peroxydisulfate to generate reactive species, including SO4•-, •OH, O2•- and 1O2, which could degrade sulfamethoxazole. Secondly, the oxygen vacancies could modulate intrinsic electrons, resulted in the surface activation of catalyst and accelerated charge transfer, which was favorable for the degradation of sulfamethoxazole. Thirdly, the presence of vitamin C not only promoted the formation of oxygen vacancies but also expanded the interlayer spacing of layered double hydroxide. A large interlayer spacing facilitated the diffusion of peroxydisulfate and pollutants in the interlayer and improved the utilization efficiency of the active site. Lastly, the high-valent cobalt species exhibited excellent oxidation ability and enhanced the catalyst performance through continuously being employed as an electron acceptor. This study provided a valuable insight for the design and application of Co-based catalysts in peroxydisulfate-based advanced oxidation processes.


Assuntos
Oxigênio , Sulfametoxazol , Sulfametoxazol/química , Oxigênio/química , Cobalto/química , Ácido Ascórbico , Carvão Mineral , Hidróxidos/química , Vitaminas
17.
J Hazard Mater ; 465: 133424, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38185088

RESUMO

Heavy metal pollution poses a major threat to human health, and developing a user-deliverable heavy metal detection strategy remains a major challenge. In this work, two-mode Hg2+ sensing platforms based on the tunable cobalt metal-organic framework (Co-MOF) active site strategy are constructed, including a colorimetric, and an electrochemical assay using a personal glucose meter (PGM) as the terminal device. Specifically, thymine (T), a single, adaptable nucleotide, is chosen to replace typical T-rich DNA aptamers. The catalytic sites of Co-MOF are tuned competitively by the specific binding of T-Hg2+-T, and different signal output platforms are developed based on the different enzyme-like activities of Co-MOF. DFT calculations are utilized to analyze the interaction mechanism between T and Co-MOF with defect structure. Notably, the two-mode sensing platforms exhibit outstanding detection performance, with LOD values as low as 0.5 nM (colorimetric) and 3.69 nM (PGM), respectively, superior to recently reported nanozyme-based Hg2+ sensors. In real samples of tap water and lake water, this approach demonstrates an effective recovery rate and outstanding selectivity. Surprisingly, the method is potentially versatile and, by exchanging out T-Hg2+-T, can also detect Ag+. This simple, portable, and user-friendly Hg2+ detection approach shows plenty of promise for application in the future.


Assuntos
Mercúrio , Estruturas Metalorgânicas , Humanos , Estruturas Metalorgânicas/química , Domínio Catalítico , Cobalto/química , Água/química , Mercúrio/química , Colorimetria
18.
Biol Trace Elem Res ; 202(2): 765-777, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37191761

RESUMO

Cobalt ferrite nanoparticles (CFN) are employed in data storage, imaging, medication administration, and catalysis due to their superparamagnetic characteristics. The widespread use of CFN led to significantly increased exposure to people and the environment to these nanoparticles. Until now, there is not any published paper describing the adverse effect of repeated oral intake of this nanoformulation on rats' lungs. So, the current research aims to elucidate the pulmonary toxicity prompted by different concentrations of CFN in rats as well as to explore the mechanistic way of such toxicity. We used 28 rats that were divided equally into 4 groups. The control group received normal saline, and the experimental groups received CFN at dosage levels 0.05, 0.5, and 5 mg/kg bwt. Our findings revealed that CFN enhanced dose-dependent oxidative stress manifested by raising in the MDA levels and declining in the GSH content. The histopathological examination revealed interstitial pulmonary inflammation along with bronchial and alveolar damage in both 0.5 and 5 mg CFN given groups. All these lesions were confirmed by the immunohistochemical staining that demonstrated strong iNOS and Cox-2 protein expression. There was also a significant upregulation of TNFα, Cox-2, and IL-1ß genes with downregulation of IL-10 and TGF-ß genes. Additionally, the group receiving 0.05 mg CFN did not exhibit any considerable toxicity in all measurable parameters. We concluded that the daily oral intake of either 0.5 or 5 mg CFN, but not 0.05 mg, could induce pulmonary toxicity via NPs and/or its leached components (cobalt and iron)-mediated oxido-inflammatory stress. Our findings may help to clarify the mechanisms of pulmonary toxicity generated by these nanoparticles through outlining the standards for risk assessment in rats as a human model.


Assuntos
Pneumopatias , Nanopartículas , Pneumonia , Humanos , Ratos , Animais , Ciclo-Oxigenase 2 , Pneumonia/induzido quimicamente , Nanopartículas/toxicidade , Cobalto/química , Estresse Oxidativo
19.
Chemistry ; 30(4): e202302484, 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-37870209

RESUMO

Cobaltabis(dicarbollides), ferrabis(dicarbollide), and their halogenated derivatives are the most studied metallacarboranes with great medical potential. These versatile compounds and their iodinated derivatives can be used in chemotherapy, radiotherapy, particle therapy, and bioimaging when isotopes are used. These metallacarboranes have been evaluated in vitro and recently in vivo with complex animal models. Lately, these studies have been complemented using the invertebrate Caenorhabditis elegans (C. elegans), a nematode largely used in toxicology. When evaluated at the L4 stage, cobaltabis(dicarbollides), ([o-COSAN]- and [8,8'-I2 -o-COSAN]- ), exhibited a higher mean lethal dose (LD50 ) than ferrabis(dicarbollides) ([o-FESAN]- and [8,8'-I2 -o-FESAN]- ). In this work, we used the C. elegans embryos since they are a complex biological barrier with concentric layers of polysaccharides and proteins that protect them from the environment. We assessed if the metal atom changes their biointeraction with the C. elegans embryos. First, we assessed the effects on embryo development for metallacarboranes and their di-iodinated derivatives. We observed changes in color and in their surface structure. An exhaustive physicochemical characterization was performed to understand better this interaction, revealing a stronger interaction of ferrabis(dicarbollide) compounds with C. elegans embryos than the cobaltabis(dicarbollide) molecules. Unveiling the biological interaction of these compounds is of great interest for their future biomedical applications.


Assuntos
Ânions , Caenorhabditis elegans , Compostos Organometálicos , Animais , Metais , Compostos Organometálicos/química , Cobalto/química
20.
Food Chem ; 439: 138073, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38029564

RESUMO

This study introduces an efficient electrochemical method for rapidly identifying the pathogen Pseudomonas aeruginosa (P. aeruginosa), which poses threats to individuals with compromised immune systems and cystic fibrosis. Unlike conventional techniques such as polymerase chain reaction, which fails to detect modifications in the resistant properties of microbes due to environmental stress, our proposed electrochemical approach offers a promising alternative. The characterisation analyses, involving microscopic and spectroscopic methods, reveal that the nanocomposite exhibits a crystalline structure, specific atomic vibrational patterns, a cubic surface shape, and distinct elemental compositions. This sensor demonstrates exceptional detection capabilities for P. aeruginosa, with a linear range of 1-23 CFU mL-1 and a low detection limit of 4.0 × 10-3 CFU mL-1. This research not only explores novel electrochemical techniques and the CoFe2O4/AgNPs nanocomposite but also their practical implications in food science, highlighting their relevance across various food samples, water, and soil.


Assuntos
Nanopartículas Metálicas , Nanocompostos , Humanos , Prata/química , Pseudomonas aeruginosa , Técnicas Eletroquímicas/métodos , Cobalto/química , Nanocompostos/química , Nanopartículas Metálicas/química
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