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1.
J Biomed Mater Res B Appl Biomater ; 112(8): e35459, 2024 Aug.
Article in English | MEDLINE | ID: mdl-39082218

ABSTRACT

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanofibers embedded with borate glasses of 45B5 composition doped with Co2+, Cu2+, and Zn2 +(46.1 B2O326.9-X CaO24.4 Na2O2.6 P2O5, X CoO/CuO/ZnO mol % (X = 0-5)) were produced by electrospinning for wound healing applications. Prior to their addition, the glasses exhibited two broad halos typical of a vitreous borate network, which were mainly composed of ring-type metaborate structural units. The particle distribution in the PHBV nanofibers embedded with 45B5 borate bioactive glasses is present in isolated and agglomerated states, being partially coated by a polymeric layer-except for the cobalt-doped glass, which resulted in a successful encapsulation with 100% embedding efficiency. The incorporation of the glasses reduced the PHBV crystallinity degree and its decomposition temperature, as well as its mechanical properties, including Young's modulus, tensile strength, and elongation at break. The neat PHBV fibers and those containing the cobalt-doped glasses demonstrated great cytocompatibility with human keratinocytes (HaCat), as suggested by the high cell viability after 7 days of exposure. Further studies are needed to fully understand the wound healing potential of these fibers, but our results significantly contribute to the area.


Subject(s)
Bandages , Borates , Cobalt , Copper , Polyesters , Zinc , Humans , Copper/chemistry , Cobalt/chemistry , Polyesters/chemistry , Borates/chemistry , Zinc/chemistry , Glass/chemistry , Materials Testing , Wound Healing , Nanofibers/chemistry , Cell Line , Polyhydroxybutyrates
2.
J Photochem Photobiol B ; 258: 112991, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39033547

ABSTRACT

INTRODUCTION: Cardiovascular diseases are the leading cause of morbidity and mortality worldwide. Ischemic heart disease is one of the most harmful conditions to cellular structure and function. After reperfusion treatment, a spectrum of adverse effects becomes evident, encompassing altered cell viability, heightened oxidative stress, activated autophagy, and increased apoptosis. Photobiomodulation (PBM) has been utilized in experimental models of cardiac hypoxia to enhance mitochondrial response and ameliorate biochemical changes in injured tissue. However, the effects of PBM on cultured cardiomyocytes subjected to hypoxia/reoxygenation are not yet well established. METHOD: H9C2 cardiomyocytes were exposed to hypoxia with concentrations of 300 µM CoCl2 for 24 h, followed by 16 h of reoxygenation through incubation in a normoxic medium. Treatment was conducted using GaAIAs Laser (850 nm) after hypoxia at an intensity of 1 J/cm2. Cells were divided into three groups: Group CT (cells maintained under normoxic conditions), Group HR (cells maintained in hypoxia and reoxygenation conditions without treatment), Group HR + PBM (cells maintained in hypoxia and reoxygenation conditions that underwent PBM treatment). Cell viability was analyzed using MTT, and protein expression was assessed by western blot. One-way ANOVA with the Tukey post hoc test was used for data analysis. Differences were significant when p < 0.05. RESULTS: PBM at an intensity of 1 J/cm2 mitigated the alterations in cell survival caused by hypoxia/reoxygenation. Additionally, it significantly increased the expression of proteins Nrf2, HSP70, mTOR, LC3II, LC3II/I, and Caspase-9, while reducing the expression of PGC-1α, SOD2, xanthine oxidase, Beclin-1, LC3I, and Bax. CONCLUSION: PBM at intensities of 1 J/cm2 reverses the changes related to oxidative stress, mitochondrial biogenesis, autophagy, and apoptosis caused by hypoxia and reoxygenation in a culture of cardiomyocytes.


Subject(s)
Apoptosis , Autophagy , Cell Hypoxia , Cell Survival , Myocytes, Cardiac , Oxidative Stress , Myocytes, Cardiac/radiation effects , Myocytes, Cardiac/cytology , Myocytes, Cardiac/metabolism , Cell Survival/radiation effects , Animals , Rats , Cell Line , Cell Hypoxia/radiation effects , Autophagy/radiation effects , Oxidative Stress/radiation effects , Apoptosis/radiation effects , Low-Level Light Therapy , Oxygen/metabolism , Cobalt/chemistry , Peroxisome Proliferator-Activated Receptor Gamma Coactivator 1-alpha/metabolism , NF-E2-Related Factor 2/metabolism
3.
Int J Mol Sci ; 25(13)2024 Jun 27.
Article in English | MEDLINE | ID: mdl-39000155

ABSTRACT

Transition metal oxides are a great alternative to less expensive hydrogen evolution reaction (HER) catalysts. However, the lack of conductivity of these materials requires a conductor material to support them and improve the activity toward HER. On the other hand, carbon paste electrodes result in a versatile and cheap electrode with good activity and conductivity in electrocatalytic hydrogen production, especially when the carbonaceous material is agglomerated with ionic liquids. In the present work, an electrode composed of multi-walled carbon nanotubes (MWCNTs) and cobalt ferrite oxide (CoFe2O4) was prepared. These compounds were included on an electrode agglomerated with the ionic liquid N-octylpyridinium hexafluorophosphate (IL) to obtain the modified CoFe2O4/MWCNTs/IL nanocomposite electrode. To evaluate the behavior of each metal of the bimetallic oxide, this compound was compared to the behavior of MWCNTs/IL where a single monometallic iron or cobalt oxides were included (i.e., α-Fe2O3/MWCNTs/IL and Co3O4/MWCNTs/IL). The synthesis of the oxides has been characterized by X-ray diffraction (XRD), RAMAN spectroscopy, and field emission scanning electronic microscopy (FE-SEM), corroborating the nanometric character and the structure of the compounds. The CoFe2O4/MWCNTs/IL nanocomposite system presents excellent electrocatalytic activity toward HER with an onset potential of -270 mV vs. RHE, evidencing an increase in activity compared to monometallic oxides and exhibiting onset potentials of -530 mV and -540 mV for α-Fe2O3/MWCNTs/IL and Co3O4/MWCNTs/IL, respectively. Finally, the system studied presents excellent stability during the 5 h of electrolysis, producing 132 µmol cm-2 h-1 of hydrogen gas.


Subject(s)
Cobalt , Ferric Compounds , Hydrogen , Ionic Liquids , Nanocomposites , Nanotubes, Carbon , Oxides , Cobalt/chemistry , Nanotubes, Carbon/chemistry , Ionic Liquids/chemistry , Nanocomposites/chemistry , Catalysis , Hydrogen/chemistry , Ferric Compounds/chemistry , Oxides/chemistry , Electrodes , Electrochemical Techniques/methods , X-Ray Diffraction , Spectrum Analysis, Raman
4.
Environ Sci Pollut Res Int ; 31(19): 28025-28039, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38523211

ABSTRACT

Azo dyes, widely used in the textile industry, contribute to effluents with significant organic content. Therefore, the aim of this work was to synthesize cobalt ferrite (CoFe2O4) using the combustion method and assess its efficacy in degrading the azo dye Direct Red 80 (DR80). TEM showed a spherical structure with an average size of 33 ± 12 nm. Selected area electron diffraction and XRD confirmed the presence of characteristic crystalline planes specific to CoFe2O4. The amount of Co and Fe metals were determined by ICP-OES, indicating an n(Fe)/n(Co) ratio of 2.02. FTIR exhibited distinct bands corresponding to Co-O (455 cm-1) and Fe-O (523 cm-1) bonds. Raman spectroscopy detected peaks associated with octahedral and tetrahedral sites. For the first time, the material was applied to degrade DR80 in an aqueous system, with the addition of persulfate. Consistently, within 60 min, these trials achieved nearly 100% removal of DR80, even after the material had undergone five cycles of reuse. The pseudo-second-order model was found to be the most fitting model for the experimental data (k2 = 0.07007 L mg-1 min-1). The results strongly suggest that degradation primarily occurred via superoxide radicals and singlet oxygen. Furthermore, the presence of UV light considerably accelerated the degradation process (k2 = 1.54093 L mg-1 min-1). The material was applied in a synthetic effluent containing various ions, and its performance consistently approached 100% in the photo-Fenton system. Finally, two degradation byproducts were identified through HPLC-MS/MS analysis.


Subject(s)
Cobalt , Ferric Compounds , Singlet Oxygen , Cobalt/chemistry , Ferric Compounds/chemistry , Singlet Oxygen/chemistry , Superoxides/chemistry , Azo Compounds/chemistry , Water Pollutants, Chemical/chemistry , Coloring Agents/chemistry , Iron/chemistry , Hydrogen Peroxide/chemistry
5.
J Biomed Mater Res B Appl Biomater ; 112(1): e35319, 2024 01.
Article in English | MEDLINE | ID: mdl-37610175

ABSTRACT

Cobalt-doped monetite powders were synthesized by coprecipitation method under a cobalt nominal content between 2 and 20 mol % of total cation. Structural characterization of samples was performed by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy. XRD results indicated that the Co-doped samples exhibited a monetite single-phase with the cell parameters and crystallite size dependent on the amount of substitutional element incorporated into the triclinic crystalline structure. Cell viability and adhesion assays using pre-osteoblastic cells showed there is no toxicity and the RTqPCR analysis showed significant differences in the expression for osteoblastic phenotype genes, showing a potential material for the bone regeneration.


Subject(s)
Calcium Phosphates , Cobalt , Cobalt/pharmacology , Cobalt/chemistry , Bone Regeneration , X-Ray Diffraction , Spectroscopy, Fourier Transform Infrared
6.
J Trace Elem Med Biol ; 82: 127341, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38091868

ABSTRACT

Given the importance of the endothelial cell phenotype in dental peri-implant healing processes, the aim of this study was to better assess the involvement of endothelial cells responding to cobalt-chromium (CoCr)-enriched medium. Biologically, cobalt is widely used molecule to induce chemical experimental hypoxia because it stabilizes hypoxia inducible factors (HIF1α). The aplication of hypoxia models provides better experimental condition to allow its impact on cellular metabolism, by looking for biochemical and molecular issues. Thus, this study looks for understaing whether CoCr-based materials are able to modulate endothelial cells considering the hypoxic effect prmoted by cobalt. Firstly, our data shows there is a siginificant effect on endothelial phenotype by modulating the expression of VEGF and eNOS genes, whith low requirement of genes related with proteasome intracellular complex. Importantly, the data were validated using classical chemical modulators of hypoxia signaling [chrysin (5,7-dihydroxyflavone) and Dimethyloxalylglycine (DMOG)] in functional assays. Altogether, these data validate the hypothesis that hipoxya is important to maintain the phenotype of endothelial cells, and it is properly interesting during the tissue regeneration surrounding implants and so compromising osseointegration process. Finally, it is important to mention that the cobalt released from CoCr devices might contribute with an sufficient microenvironment surrounding implanted devices and it paviments new roads looking for more bioactive surfaces of implantable materials in human health.


Subject(s)
Chromium , Endothelial Cells , Humans , Chromium/chemistry , Cobalt/pharmacology , Cobalt/chemistry , Signal Transduction
7.
Pesqui. bras. odontopediatria clín. integr ; 24: e220128, 2024. tab, graf
Article in English | LILACS, BBO - Dentistry | ID: biblio-1535006

ABSTRACT

ABSTRACT Objective: To assess the effects of cobalt chloride (CoCl2) as a hypoxia mimicking agent on human umbilical cord mesenchymal stem cells (hUCMSCs) expression of HIF-1α and mTOR for use in regenerative dentistry. Material and Methods: Human umbilical cord mesenchymal stem cells were isolated and then cultured. The characteristics of stemness were screened and confirmed by flow cytometry. The experiment was conducted on hypoxia (H) and normoxia (N) groups. Each group was divided and incubated into 24-, 48-, and 72-hours observations. Hypoxic treatment was performed using 100 µM CoCl2 on 5th passage cells in a conventional incubator (37°C; 5CO2). Then, immunofluorescence of HIF-1α and mTOR was done. Data was analyzed statistically using One-way ANOVA and Tukey's HSD. Results: Significant differences were found between normoxic and hypoxic groups on HIF-1α (p=0.015) and mTOR (p=0.000) expressions. The highest HIF-1α expression was found at 48 hours in the hypoxia group, while for mTOR at 24 hours in the hypoxia group. Conclusion: Hypoxia using cobalt chloride was able to increase human umbilical cord mesenchymal stem cells expression of HIF-1α and mTOR.


Subject(s)
Humans , Umbilical Cord/cytology , Chlorides/chemistry , Cobalt/chemistry , Mesenchymal Stem Cells/cytology , Hypoxia/pathology , Analysis of Variance , Flow Cytometry
8.
Int J Mol Sci ; 24(14)2023 Jul 24.
Article in English | MEDLINE | ID: mdl-37511597

ABSTRACT

Additive manufacturing and nanotechnology have been used as fundamental tools for the production of nanostructured parts with magnetic properties, expanding the range of applications in additive processes through tank photopolymerization. Magnetic cobalt ferrite (CoFe2O4) and barium ferrite (BaFe12O19) nanoparticles (NPs) with an average size distribution value (DTEM) of 12 ± 2.95 nm and 37 ± 12.78 nm, respectively, were generated by the hydroxide precipitation method. The dispersion of the NPs in commercial resins (Anycubic Green and IRIX White resin) was achieved through mechanochemical reactions carried out in an agate mortar for 20 min at room temperature, with limited exposure to light. The resulting product of each reaction was placed in amber vials and stored in a box to avoid light exposure. The photopolymerization process was carried out only at low concentrations (% w/w NPs/resin) since high concentrations did not result in the formation of pieces, due to the high refractive index of ferrites. The Raman spectroscopy of the final pieces showed the presence of magnetic NPs without any apparent chemical changes. The electron paramagnetic resonance (EPR) results of the pieces demonstrated that their magnetic properties were maintained and not altered during the photopolymerization. Although significant differences were observed in the dispersion process of the NPs in each piece, we determined that the photopolymerization did not affect the structure and superparamagnetic behavior of ferrite NPs during processing, successfully transferring the magnetic properties to the final 3D-printed piece.


Subject(s)
Nanoparticles , Nanostructures , Nanoparticles/chemistry , Cobalt/chemistry , Ferric Compounds/chemistry , Magnetics , Magnetic Phenomena
9.
Org Lett ; 25(19): 3451-3455, 2023 05 19.
Article in English | MEDLINE | ID: mdl-37141632

ABSTRACT

We designed and executed an expedient synthesis of a complex analogue of the potent immunosuppressive natural product brasilicardin A. Our successful synthesis featured application of our recently developed MHAT-initiated radical bicyclization, which delivered the targeted, complex analogue in 17 steps in the longest linear sequence. Unfortunately, this analogue showed no observable immunosuppressive activity, which speaks to the importance of the structural and stereochemical elements of the natural core scaffold.


Subject(s)
Cobalt , Immunosuppressive Agents , Cobalt/chemistry , Catalysis
10.
Environ Technol ; 44(19): 2900-2912, 2023.
Article in English | MEDLINE | ID: mdl-35220916

ABSTRACT

With a worldwide ever increasing demand for metals, particularly for the manufacture of electronics and batteries, there is not only a concurrent need to recover these materials from their subsequent waste streams but also a need to make advancements to do this via development of more efficient and eco-friendly processes for metal recovery; solid-phase extraction can be considered a promising alternative to conventional processes. This work studied the production of novel nanofibers modified with Cyanex 272 and their application in the recovery of cobalt present in aqueous solution The nanofibers produced by forcespinning were characterized by SEM, FT-IR and TGA and the extraction of cobalt was evaluated by variation of the pH, solid:liquid (S:L) ratio, extraction time and Cyanex 272 content in the nanofibers. The best extraction efficiency was 99.96%, achieved under the following conditions: pH 8; (S:L) ratio of 1:200; 25% of Cyanex 272; Extraction time of 60 min. The maximum extraction capacity obtained was 15.46 mg Co/g of nanofiber and 70.15 mg Co/g of extractor. In successive reuse cycles, the results demonstrated that the extraction efficiency was maintained at over 85%. The findings showed that Nylon 6/Cyanex 272 nanofibers are a new robust and promising material for the recovery of heavy metals from aqueous solution, confirming that nanofibers have an efficiency similar to conventional liquid-liquid extraction, without the disadvantage of volatile organic compounds emissions generated by the use of organic diluents.


Subject(s)
Cobalt , Nanofibers , Cobalt/chemistry , Spectroscopy, Fourier Transform Infrared , Metals , Water
11.
Molecules ; 27(21)2022 Oct 26.
Article in English | MEDLINE | ID: mdl-36364105

ABSTRACT

The C-X bond cleavage in different methyl halides (CH3X; X = Cl, Br, I) mediated by 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(II) (CoIICbx) was theoretically investigated in the present work. An SN2-like mechanism was considered to simulate the chemical process where the cobalt atom acts as the nucleophile and the halogen as the leaving group. The reaction path was computed by means of the intrinsic reaction coordinate method and analyzed in detail through the reaction force formalism, the quantum theory of atoms in molecules (QTAIM), and the calculation of one-electron density derived quantities, such as the source function (SF) and the spin density. A thorough comparison of the results with those obtained in the same reaction occurring in presence of 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(I) (CoICbx) was conducted to reveal the main differences between the two cases. The reactions mediated by CoIICbx were observed to be endothermic and possess higher activation energies in contrast to the reactions where the CoICbx complex is present. The latter was supported by the reaction force results, which suggest a relationship between the activation energy and the ionization potentials of the different nucleophiles present in the cleavage reaction. Moreover, the SF results indicates that the lower axial ligand (i.e., 5,6-dimethylbenzimidazole) exclusively participates on the first stage of the reaction mediated by the CoIICbx complex, while for the CoICbx case, it appears to have an important role along the whole process. Finally, the QTAIM charge analysis indicates that oxidation of the cobalt atom occurs in both cases; at the same time, it suggests the formation of an uncommon two-center one-electron bond in the CoIICbx case. The latter was confirmed by means of electron localization calculations, which resulted in a larger electron count at the Co-C interatomic region for the CoICbx case upon comparison with its CoIICbx counterpart.


Subject(s)
Cobalt , Quantum Theory , Cobalt/chemistry , Models, Theoretical , Ligands , Electrons
12.
J. oral res. (Impresa) ; 11(5): 1-12, nov. 23, 2022. ilus, tab
Article in English | LILACS | ID: biblio-1435341

ABSTRACT

In Purpose: The fabrication technique can influence the mechanical properties of Cobalt-Chromium (Co-Cr) dental alloys. Hence, the present study aims to determine the corrosion resistance and thermal expansion of alloys manufactured using three contemporary techniques. Material and Methods: A total of nine specimens of Co-Cr alloy were prepared according to ISO 22674 by each one of the three manufacturing processes (three in each process); conventional casting, direct metal laser sintering (DMLS) and milling (MIL). All these specimens were tested for coefficient of thermal expansion and corrosion resistance. The data was tabulated and analyzed statistically. Results: The difference in the thermal expansion of alloys fabricated using three techniques was non-significant at almost all the temperatures from 50 ºC to 950 ºC (p>0.05), except 450 ºC and 600 °C. The polarization resistance of specimens manufactured using the conventional method was more compared to DMLS and MIL at pH 5 (Conventional>MIL>DMLS) (p<0.001). Conclusion: The thermal expansion behavior of alloys manufactured using the three selected techniques were similar, whereas, at acidic pH, the corrosion resistance of conventional and MIL were better than the DMLS.


Antecedentes: La técnica de fabricación puede influir en las propiedades mecánicas de las aleaciones dentales de cobalto-cromo (Co-Cr). Por lo tanto, el presente estudio tiene como objetivo determinar la resistencia a la corrosión y la expansión térmica de aleaciones fabricadas con tres técnicas contemporáneas. Material y Métodos: Se prepararon un total de nueve probetas de aleación de Co-Cr según ISO 22674 por cada uno de los tres procesos de fabricación (tres en cada proceso); fundición convencional, sinterización directa de metal por láser (DMLS) y fresado (MIL). Todos estos especímenes fueron probados para determinar el coeficiente de expansión térmica y la resistencia a la corrosión. Los datos fueron tabulados y analizados estadísticamente. Resultados: La diferencia en la dilatación térmica de las aleaciones fabricadas con las tres técnicas no fue significativa en casi todas las temperaturas desde 50ºC hasta 950ºC (p>0,05), excepto 450ºC y 600ºC. La resistencia a la polarización de las muestras fabricadas con el método convencional fue mayor en comparación con DMLS y MIL a pH 5 (Convencional>MIL>DMLS) (p<0, 0 01). Conclusión: El comportamiento de expansión térmica de las aleaciones fabricadas con las tres técnicas seleccionadas fue similar, mientras que, a pH ácido, la resistencia a la corrosión de la convencional y la MIL fue mejor que la de la DMLS.


Subject(s)
Humans , Temperature , Chromium Alloys , Corrosion , Dental Alloys , Surface Properties , In Vitro Techniques , Chromium/chemistry , Cobalt/chemistry , Lasers
13.
Molecules ; 27(14)2022 Jul 19.
Article in English | MEDLINE | ID: mdl-35889469

ABSTRACT

A new supramolecular electrocatalyst for Oxygen Evolution Reaction (OER) was synthesized from a central multibridging cobalt tetrapyridylporphyrazine (CoTPyPz) species by attaching four [Ru(bpy)2Cl]+ groups. Both CoTPyPz and the tetraruthenated cobalt porphyrazine species, TRuCoTPyPz, form very homogenous molecular films just by dropcasting their methanol solutions onto GCE electrodes. Such films exhibited low overpotentials for O2 evolution, e.g., 560 e 340 mV, respectively, displaying high stability, typically exceeding 15 h. The kinetic parameters obtained from the Tafel plots showed that the peripheral complexes are very important for the electrocatalytic activity. Hyperspectral Raman images taken along the electrochemical process demonstrated that the cobalt center is the primary active catalyst site, but its performance is enhanced by the ruthenium complexes, which act as electron-donating groups, in the supramolecular system.


Subject(s)
Cobalt , Ruthenium , Catalysis , Cobalt/chemistry , Electrons , Oxygen/chemistry
14.
Mikrochim Acta ; 189(8): 269, 2022 07 05.
Article in English | MEDLINE | ID: mdl-35788785

ABSTRACT

The synthesis and characterization of a novel titania/silica hybrid xerogel subsequently modified with 4-methylpyridine (4-Pic), named TiSi4Pic+Cl- is reported. The physicochemical, structural and thermal properties of TiSi4Pic+Cl- were characterized using several techniques. Anchoring cobalt(II) phthalocyanine (CoTsPc) in TiSi4Pic+Cl- showed greater electroanalytical sensitivity over other sensors built with these materials. A novel electroanalytical method was developed to quantify the noxious biocide pentachlorophenol (PCP) for environmental monitoring. The peak current intensity increased linearly with the analyte concentration in the range between 0.99 and 4.21 µmol L-1, based on the oxidation process (at + 0.81 V, vs. Ag/AgCl) of differential pulse voltammetry (DPV). The estimated limit of detection (LOD) was 29 nmol L-1. Recovery tests in environmental samples showed a PCP concentration of 2.05 ± 0.03 µmol L-1 (n = 3). The method was statistically validated by comparing the PCP concentrations with those obtained by molecular absorption spectrometry and high-performance liquid chromatography-diode array detection (HPLC-DAD). At a 95% confidence level, no difference between the results was found, therefore confirming the excellent accuracy of the proposed method.


Subject(s)
Pentachlorophenol , Cobalt/chemistry , Electrodes , Indoles , Isoindoles , Silicon Dioxide , Titanium
15.
J Inorg Biochem ; 233: 111854, 2022 08.
Article in English | MEDLINE | ID: mdl-35636301

ABSTRACT

Helical complexes composed of organic ligand strands and metallic centers, called helicates, present interactions with biomacromolecules, such as deoxyribonucleic acid, as one of their main biological applications in bioinorganic chemistry. Despite the potential antineoplastic and antibacterial results of the interactions between helicates and biomacromolecules, there is still a gap of research in the literature, primarily in terms of solubility in aqueous media. In this study, we present the synthesis, structural analysis, and interaction with biomacromolecules of two water-soluble cobalt(II) double-stranded helicates: [CoII2L22][CoII(NCS)4]∙9H2O (C1) and [CoII2L42]Cl2∙11H2O (C2). These complexes are obtained from iminic ligands (L2 and L4) derived from pyridoxal, a vitamin B6 aldehyde derivative. Through spectroscopic assays, these helical complexes were shown to have weak and moderate binding capacities with calf-thymus deoxyribonucleic acid and human serum albumin, respectively. The theoretical assays suggest that C1 and C2 interact with the minor groove of deoxyribonucleic acid and have different main binding sites with human serum albumin. Furthermore, Van der Waals and hydrogen bonds were shown to be the main intermolecular forces for these C1-C2:biomacromolecules interactions.


Subject(s)
Cobalt , Pyridoxal , Cobalt/chemistry , DNA/chemistry , Humans , Ligands , Serum Albumin, Human , Water/chemistry
16.
Sci Rep ; 12(1): 3316, 2022 02 28.
Article in English | MEDLINE | ID: mdl-35228662

ABSTRACT

The new coronavirus, SARS-CoV-2, caused the COVID-19 pandemic, characterized by its high rate of contamination, propagation capacity, and lethality rate. In this work, we approach the use of phthalocyanines as an inhibitor of SARS-CoV-2, as they present several interactive properties of the phthalocyanines (Pc) of Cobalt (CoPc), Copper (CuPc) and without a metal group (NoPc) can interact with SARS-CoV-2, showing potential be used as filtering by adsorption on paints on walls, masks, clothes, and air conditioning filters. Molecular modeling techniques through Molecular Docking and Molecular Dynamics were used, where the target was the external structures of the virus, but specifically the envelope protein, main protease, and Spike glycoprotein proteases. Using the g_MM-GBSA module and with it, the molecular docking studies show that the ligands have interaction characteristics capable of adsorbing the structures. Molecular dynamics provided information on the root-mean-square deviation of the atomic positions provided values between 1 and 2.5. The generalized Born implicit solvation model, Gibbs free energy, and solvent accessible surface area approach were used. Among the results obtained through molecular dynamics, it was noticed that interactions occur since Pc could bind to residues of the active site of macromolecules, demonstrating good interactions; in particular with CoPc. Molecular couplings and free energy showed that S-gly active site residues interacted strongly with phthalocyanines with values ​​of - 182.443 kJ/mol (CoPc), 158.954 kJ/mol (CuPc), and - 129.963 kJ/mol (NoPc). The interactions of Pc's with SARS-CoV-2 may predict some promising candidates for antagonists to the virus, which if confirmed through experimental approaches, may contribute to resolving the global crisis of the COVID-19 pandemic.


Subject(s)
COVID-19 , Cobalt/chemistry , Coordination Complexes/chemistry , Copper/chemistry , Isoindoles/chemistry , Molecular Docking Simulation , Molecular Dynamics Simulation , SARS-CoV-2/chemistry , Viral Proteins/chemistry , Humans
17.
J Am Chem Soc ; 143(31): 12108-12119, 2021 08 11.
Article in English | MEDLINE | ID: mdl-34318666

ABSTRACT

High-valent multimetallic-oxo/oxyl species have been implicated as intermediates in oxidative catalysis involving proton-coupled electron transfer (PCET) reactions, but the reactive nature of these oxo species has hindered the development of an in-depth understanding of their mechanisms and multimetallic character. The mechanism of C-H oxidation by previously reported RuCo3O4 cubane complexes bearing a terminal RuV-oxo ligand, with significant oxyl radical character, was investigated. The rate-determining step involves H atom abstraction (HAA) from an organic substrate to generate a Ru-OH species and a carbon-centered radical. Radical intermediates are subsequently trapped by another equivalent of the terminal oxo to afford isolable radical-trapped cubane complexes. Density functional theory (DFT) reveals a barrierless radical combination step that is more favorable than an oxygen-rebound mechanism by 12.3 kcal mol-1. This HAA reactivity to generate organic products is influenced by steric congestion and the C-H bond dissociation energy of the substrate. Tuning the electronic properties of the cubane (i.e., spin density localized on terminal oxo, basicity, and redox potential) by varying the donor ability of ligands at the Co sites modulates C-H activations by the RuV-oxo fragment and enables construction of structure-activity relationships. These results reveal a mechanistic pathway for C-H activation by high-valent metal-oxo species with oxyl radical character and provide insights into cooperative effects of multimetallic centers in tuning PCET reactivity.


Subject(s)
Cobalt/chemistry , Coordination Complexes/chemistry , Oxygen/chemistry , Rubidium/chemistry , Density Functional Theory , Electron Transport , Molecular Conformation , Protons
18.
J Inorg Biochem ; 219: 111432, 2021 06.
Article in English | MEDLINE | ID: mdl-33873052

ABSTRACT

A series of new coordination compounds of cobalt(II), copper(II) and zinc(II) with heterocyclic ester derivatives (ethyl 4-methyl-5-imidazole-carboxylate (emizco), 1-(2-(phenylsulphonyl)ethyl)-4-imidazole carboxylate (semizco)) and methyl 5-(propylthio)-2-benzimidazolecarbamate (albendazole, abz) were synthesized. They were fully characterized by different techniques such as IR, UV-Vis-NIR, elemental analysis, molar conductivity and magnetic susceptibility. Additionally, X-ray crystal structures of semizco and its [Co(semizco)2Cl2]·2CH3CN 10, [Co(smmizco)2Br2]·2CH3CN 11 and [Cu(semizco)2Br2] 15 coordination compounds are analyzed. These compounds present lone pair SO⋯π interactions between the sulfone and the imidazolic ring. These ligands showed three coordination modes: monodentate, through an imidazolic nitrogen atom, or a bidentate chelating mode by a nitrogen and an oxygen atom from the ester group. The different coordination modes and the number of coordinated ligands gave rise to tetrahedral and octahedral compounds, or for [Cu(semizco)(µ-Br)Br]n·0.5H2O 7 a square base pyramidal geometry. A cytotoxic study was carried out with the free ligands and their copper(II) and zinc(II) halide coordination compounds on HeLa (cervix-uterine), MCF-7 (breast), HCT-15 (colon), PC3 (prostate) human carcinoma cell lines and L929 mouse fibroblast (healthy cells). A TUNEL assay (terminal deoxynucleotidyl transferase dUTP nick end labeling) was performed with the most active copper(II) compounds to determine if cell death was by apoptosis.


Subject(s)
Cell Proliferation/drug effects , Cobalt/chemistry , Coordination Complexes/pharmacology , Copper/chemistry , Esters/chemistry , Zinc/chemistry , Animals , Antineoplastic Agents/pharmacology , Apoptosis/drug effects , Carbamates/chemistry , Cell Line, Tumor , Chelating Agents/pharmacology , Coordination Complexes/chemistry , Crystallography, X-Ray/methods , Humans , Imidazoles/chemistry , In Situ Nick-End Labeling/methods , Ligands , Mice , Molecular Structure
19.
Molecules ; 26(5)2021 Feb 26.
Article in English | MEDLINE | ID: mdl-33652788

ABSTRACT

Molybdates are biocidal materials that can be useful in coating surfaces that are susceptible to contamination and the spread of microorganisms. The aim of this work was to investigate the effects of copper doping of hydrated cobalt molybdate, synthesized by the co-precipitation method, on its antibacterial activity and to elucidate the structural and morphological changes caused by the dopant in the material. The synthesized materials were characterized by PXRD, Fourier Transformed Infrared (FTIR), thermogravimetric analysis/differential scanning calorimetry (TG/DSC), and SEM-Energy Dispersive Spectroscopy (SEM-EDS). The antibacterial response of the materials was verified using the Minimum Inhibitory Concentration (MIC) employing the broth microdilution method. The size of the CoMoO4·1.03H2O microparticles gradually increased as the percentage of copper increased, decreasing the energy that is needed to promote the transition from the hydrated to the beta phase and changing the color of material. CoMoO4·1.03H2O obtained better bactericidal performance against the tested strains of Staphylococcus aureus (gram-positive) than Escherichia coli (gram-negative). However, an interesting point was that the use of copper as a doping agent for hydrated cobalt molybdate caused an increase of MIC value in the presence of E. coli and S. aureus strains. The study demonstrates the need for caution in the use of copper as a doping material in biocidal matrices, such as cobalt molybdate.


Subject(s)
Anti-Infective Agents/chemistry , Cobalt/chemistry , Copper/chemistry , Molybdenum/chemistry , Anti-Infective Agents/pharmacology , Bacterial Infections/drug therapy , Coordination Complexes/chemistry , Escherichia coli/drug effects , Humans , Metal Nanoparticles/chemistry , Microbial Sensitivity Tests , Particle Size , Staphylococcus aureus/drug effects
20.
J Biomed Mater Res A ; 109(7): 1051-1064, 2021 07.
Article in English | MEDLINE | ID: mdl-32876363

ABSTRACT

Bioactive glasses (BGs) have shown great potential for tissue regeneration and their composition flexibility allows the incorporation of different ions with physiological activities and therapeutic properties in the glass network. Among the many ions that could be incorporated, cobalt (Co) is a significant one, as it mimics hypoxia, triggering the formation of new blood vessels by the vascular endothelial growth factor A (VEGFA), due to the stabilizing effect on the hypoxia inducible factor 1 subunit alpha (HIF1A), an activator of angiogenesis-related genes, and is therefore of great interest for tissue engineering applications. However, despite its promising properties, the effects of glasses incorporated with Co on angiogenesis, through human umbilical cord vein endothelial cells (HUVECs) studies, need to be further investigated. Therefore, this work aimed to evaluate the biocompatibility and angiogenic potential of a new sol-gel BG, derived from the SiO2 -CaO-P2 O5 -CoO system. The structural evaluation showed the predominance of an amorphous glass structure, and the homogeneous presence of cobalt in the samples was confirmed. in vitro experiments showed that Co-containing glasses did not affect the viability of HUVECs, stimulated the formation of tubes and the gene expression of HIF1A and VEGFA. in vivo experiments showed that Co-containing glasses stimulated VEGFA and HIF1A expression in blood vessels and cell nuclei, respectively, in the deep dermis layer of the dorsal region of rats, featuring considerable local stimulation of the angiogenesis process due to Co-release. Co-containing glasses showed therapeutic effect, and Co incorporation is a promising strategy for obtaining materials with superior angiogenesis properties for tissue engineering applications.


Subject(s)
Biomimetic Materials/chemistry , Cobalt/chemistry , Glass/chemistry , Hypoxia-Inducible Factor 1/analysis , Neovascularization, Physiologic , Vascular Endothelial Growth Factor A/analysis , Animals , Biocompatible Materials/chemistry , Biocompatible Materials/pharmacology , Biomimetic Materials/pharmacology , Cobalt/pharmacology , Human Umbilical Vein Endothelial Cells , Humans , Male , Neovascularization, Physiologic/drug effects , Rats, Wistar
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