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1.
J Environ Manage ; 345: 118905, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37678022

RESUMO

The development of cobalt-based supported catalysts with high PMS catalytic activity and stability by adjusting the composition of the support is highly desirable yet remains scarce. In the work, a series of catalysts (Co2AlO4/Al2O3-xSiO2) were prepared by impregnation and high-temperature calcination using Al2O3-xSiO2 with a low Si-Al ratio as the support. Measurement techniques such as XRD, XPS, UV-DRS, FTIR, BET, SEM and HRTEM were used to characterize textural and chemical properties (ratio of Co3+/Co2+, specific surface area, pore size, pore volume, etc.). The ratio of Co3+/Co2+ and pore volume of Co2AlO4/Al2O3-xSiO2 can be turned by controlling the ratio of Si to Al, which are closely related to the catalytic performance and reusability of the catalysts. The optimized catalyst (Co2AlO4/Al2O3-0.25SiO2) can completely degrade 10 mg/L p-nitrophenol (PNP) in 40 min in the pH range of 3-9 with excellent reusability. The effects of several reaction parameters (i.e., PMS dosage, Co2AlO4/Al2O3-0.25SiO2 dosage, reaction temperature, initial pH value, and inorganic ions) on PNP removal were comprehensively investigated. Sulfate radical (SO4•-) and singlet oxygen (1O2) are making a major contribution to the degradation of PNP. Moreover, a millimeter-scale catalyst (CoSiAl-0.25/Al2O3 pellet) was prepared by sol adsorption and high-temperature calcination method, which maintained high oxidation activity after treatment of 18 L wastewater (PNP of 10 mg/L) in a continuous flow process. The method is simple and easy to operate on a large scale, providing a new perspective on the design and preparation of cobalt-aluminum spinel catalysts for activated PMS.


Assuntos
Alumínio , Cobalto , Cobalto/química , Óxido de Alumínio/química , Peróxidos/química
2.
Chemistry ; 29(21): e202203730, 2023 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-36689256

RESUMO

The development of potent H2 production catalysts is a key aspect in our journey toward the establishment of a sustainable carbon-neutral power infrastructure. Hydrogenase enzymes provide the blueprint for designing efficient catalysts by the rational combination of central metal core and protein scaffold-based outer coordination sphere (OCS). Traditionally, a biomimetic catalyst is crafted by including natural amino acids as OCS features around a synthetic metal motif to functionally imitate the metalloenzyme activity. Here, we have pursued an unconventional approach and implanted two distinct drug molecules (isoniazid and nicotine hydrazide) at the axial position of a cobalt core to create a new genre of synthetic catalysts. The resultant cobalt complexes are active for both electrocatalytic and photocatalytic H2 production in near-neutral water, where they significantly enhance the catalytic performance of the unfunctionalized parent cobalt complex. The drug molecules showcased a dual effect as they influence the catalytic HER by improving the surrounding proton relay along and exerting subtle electronic effects. The isoniazid-ligated catalyst C1 outperformed the nicotine hydrazide-bound complex C2, as it produced H2 from water (pH 6.0) at a rate of 3960 s-1 while exhibiting Faradaic efficiency of about 90 %. This strategy opens up newer avenues of bio-inspired catalyst design beyond amino acid-based OCS features.


Assuntos
Hidrogênio , Isoniazida , Hidrogênio/química , Prótons , Aminoácidos/química , Metais , Cobalto/química , Água
3.
Colloids Surf B Biointerfaces ; 222: 113077, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36577341

RESUMO

Magnetic hyperthermia (MH) has been studied for almost seventy-five years, but its efficacy in clinical applications is still fiercely contested. Despite this, few magnetic nanosystems are approved for clinical usage due to their strong affinity as drug carriers. The most important condition for hyperthermia applications for successful cancer therapy is magnetic nanoparticles with a controlled heating pattern (42-46 °C) for a prolonged timeframe. In the current study, cobalt-zinc nanoferrites (MNPs) having a Curie temperature of 46 â„ƒ with a tunable heating profile was loaded with Doxorubicin (DOX) through a surface conjugation technique (DOX-Cs-MNPs), and characterized by using multiple techniques. The magnetic hyterises (M-H) curves revealed the occurrence of superparamagnetism in the MNPs with extremely low coercivity; further, the DOX-loaded nanoparticles exhibited enhanced saturation magnetization. More importantly, the MNPs showed that they could maintain a therapeutic temperature for an indefinite amount of time. High drug loading affinity (86 %) was observed on MNPs with pH and temperature-controlled release. Under in vitro conditions, the biocompatible DOX-Cs-MNPs caused substantial apoptosis in MCF-7 cells (72 %) with overall cell death of < 95 %. The distinctive MNPs thus have the potential to be used in clinical applications.


Assuntos
Hipertermia Induzida , Nanopartículas de Magnetita , Neoplasias , Humanos , Zinco , Doxorrubicina/farmacologia , Doxorrubicina/química , Cobalto/farmacologia , Cobalto/química , Nanopartículas de Magnetita/química , Neoplasias/tratamento farmacológico
4.
Dalton Trans ; 52(1): 159-174, 2022 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-36475549

RESUMO

Selenium-derived electrocatalysts have been well explored for electrocatalytic hydrogen evolution reactions to mimic hydrogenase-like activity; however, the stability of these synthetic mimics is yet to be enhanced. In this study, we report the synthesis and characterization of a series of 1,10-phenanthroline-cobalt(II) phenolate selenoether complexes using 1,10-phenanthroline and 6-nitro-1,10-phenanthroline-Co(II)-dichloride and substituted bis-selenophenolate ligands. The synthesized cobalt(II) phenolate selenoether complexes have been characterized by CHN analysis, mass spectrometry, single crystal XRD, and UV-visible absorption spectroscopy. These complexes show electrocatalytic proton reduction from acetic acid at an overpotential of 0.45-0.56 V vs. Fc+/Fc and surpass previously reported selenium and sulfur-containing electrocatalysts. Furthermore, gas analysis from control potential electrolysis confirms that the cobalt(II) selenoethers act as electrocatalysts to produce H2 with a faradaic efficiency of 43-83% and show a turnover number of 3.24-58.60 molcat-1. The hydrogen evolution reaction (HER) was probed using deuterated acetic acid, which demonstrates an inverse kinetic isotopic effect (KIE) and is consistent with the formation of metal hydride intermediates. Furthermore, control experiments (post-dip analysis and multiple CV studies) have been performed to support the catalysis being due to a homogeneous process. Acid titration using UV-visible spectroscopy reveals that protonation is the prior step for electrocatalysis and assists in the formation of a cobalt hydride intermediate, which upon reaction with a proton generates hydrogen gas.


Assuntos
Hidrogenase , Selênio , Prótons , Hidrogenase/química , Cobalto/química , Hidrogênio/química
5.
Molecules ; 27(23)2022 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-36500254

RESUMO

In this study, rosemary leaf extract was effectively used to synthesize cobalt oxide nanoparticles (Co3O4 NPs) using a rapid, low-cost, and environmentally friendly approach. The prepared Co3O4 NPs were examined using various analytical techniques. However, UV spectrum analysis displayed two sharp absorption peaks at ~350 and 745 nm. The dynamic light scattering and zeta potential measurements were used to evaluate the particle size and the effective stabilization of the synthetic nanoparticles in the suspensions. A semi-triangular pyramidal shape of the Co3O4 NPs with a wide particle-size distribution could be observed in the scanning electron microscopy images. The energy-dispersive X-ray spectrum confirmed their successful synthesis, as the experimental atomic percentages agreed with the theoretical values. Moreover, X-ray diffraction analysis revealed that the synthesized Co3O4 NPs had a cubic crystalline structure corroborating that of theoretical Co3O4. Additionally, the Co3O4 NPs were not toxic at ≤62.5 µg/mL for Hep G2 and at ≤31.25 µg/mL for Mcf7. Therefore, these unique environmentally friendly Co3O4 NPs at this safe concentration could be studied in the future for their therapeutic activity.


Assuntos
Nanopartículas Metálicas , Nanopartículas Metálicas/química , Cobalto/química , Extratos Vegetais/farmacologia , Extratos Vegetais/química , Difração de Raios X , Antibacterianos/química
6.
J Environ Manage ; 312: 114919, 2022 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-35358846

RESUMO

The development of cost-effective and applied catalysts for organic pollutants degradation is the cornerstone for the future valorizations of these hazardous wastes. Garlic peel was employed as solid support for the assembly of cobalt nanoparticles and was further applied for the catalytic degradation of 4-nitrophenol, bromophenol blue, and a mixture of both. A Cobalt@garlic peel nanocomposite with the morphology of semi-spherical and randomly distributed nanoparticles was prepared without the aid of any hazardous chemicals. The functional groups facilitated the adsorption of cobalt ions onto the surface of garlic peel through van der Waals forces and/or hydrogen bonds. The catalytic experiments were carried out under different operational parameters including pollutant concentration, catalytic dosage, and pH value to identify the optimal conditions for the model solutions. The results showed that the optimal pH for 4-nitrophenol degradation was around 9 and the maximum rate constant 4.56 × 10-3 sec-1. The most prominent feature of the proposed catalyst is the easy/efficient recovery and recycling of the nanoparticles from the reacting medium. This work provided a simple method for designing other similar biomass-stabilized nanocatalysts which might sharply reduce the catalytic treatment costs and broaden the scope of applications.


Assuntos
Poluentes Ambientais , Alho , Nanocompostos , Adsorção , Catálise , Cobalto/química , Poluentes Ambientais/química
7.
J Environ Manage ; 310: 114702, 2022 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-35184008

RESUMO

A novel composite catalyst prepared by fixing cobalt aluminate (CoAl2O4) spinel on formed alumina carrier by impregnation-calcination route is reported, which can be used to efficiently activate peroxymonosulfate (PMS) to degrade p-nitrophenol (PNP). The internal laws of phase composition and preparation conditions are explored in detail, and the results show that the introduction of additional aluminum ions in the preparation process changes the coordination environment and the electronic state of cobalt ions, which leads to the transformation of spinel/inverted spinel in the composition, and further affects the activity and stability of the catalyst. The selected CoAl-Aaps-600 catalyst has high CoAl2O4 content, showing good cycle performance and low cobalt leaching, and has great catalytic degradation performance at different temperatures and a wide pH range. Most notably, a fixed bed reactor packed with 20 g of CoAl-Aaps-600 exhibits excellent capacity to continuously treat 60 L of PNP solution with acceptable PNP removal ratio and low cobalt leaching content. Sulfate radical and singlet oxygen are identified as the main reactive oxygen species produced in CoAl-Aaps-600/PMS system, and the reaction mechanism is reasonably inferred. This work provides a potential application material and process for the treatment of continuous organic wastewater.


Assuntos
Carvão Mineral , Cobalto , Óxido de Alumínio , Cobalto/química , Óxido de Magnésio , Peróxidos/química
8.
Chemosphere ; 294: 133565, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35041818

RESUMO

Cobalt-zinc ferrite nanoparticles were synthesized using environmentally friendly approach with quince extract as a reducing agent. Crystal structure and morphology of the obtained materials were studied by XRD, SEM-EDS, Mössbauer and IR spectroscopy. The synthesized nanoparticles have a cubic spinel structure and crystallite size ranging from 5 to 9 nm. The infrared spectra contain characteristic absorption bands for the MA-O (∼560 cm-1) and MB-O bonds (∼420 cm-1). Force constants were calculated for both tetrahedral and octahedral bonds. As the Co content increases, the force constant for the tetrahedral bond increases and the force constant for the octahedral bond decreases. The obtained ferrite nanoparticles have good magnetization as shown by VSM (in the range from 36 to 67 emu/g). Magnetic nanoparticles CoxZn1-xFe2O4 were also tested for induction heating with electromagnetic field. The sample with x (Co) = 0.4 has the highest specific absorption rate. The synthesized samples were tested as adsorbents using the Congo Red dye as model pollutant. The best adsorbent was pure zinc ferrite with the adsorption capacity of 24.7 mg/g. The catalytic activity of the obtained ferrites for the decomposition of H2O2 was studied as well. The most active catalyst was pure cobalt ferrite. Probably, the active centers are octahedral cobalt ions. Thus, the obtained magnetic nanoparticles can be used for the adsorptive removal of pollutants, catalytic decomposition of the H2O2 and low-frequency hyperthermia.


Assuntos
Recuperação e Remediação Ambiental , Rosaceae , Adsorção , Cobalto/química , Compostos Férricos , Peróxido de Hidrogênio , Extratos Vegetais , Zinco/análise
9.
Food Chem Toxicol ; 159: 112725, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34856315

RESUMO

Synthetic food colorants are extensively used across the globe regardless of the fact that they induce deleterious side effects when used in higher amounts. In this work, a novel electrochemical sensor based on nickel nanoparticles doped lettuce-like Co3O4 anchored graphene oxide (GO) nanosheets was developed for effective detection of sulfonated azo dye sunset yellow widely used as a food colorant. Hydrothermal synthesis was adopted for the preparation of lettuce-like spinel Co3O4 nanoparticles and Ni-Co3O4 NPs/GO nanocomposite was prepared using ecofriendly and economical sonochemical method. The prepared ternary nanocomposite meticulously fabricated on a screen-printed carbon electrode exhibited remarkable electrocatalytic activity towards sunset yellow determination. This is apparent from the resultant well-defined and intense redox peak currents of Ni-Co3O4 NPs/GO nanocomposite modified electrode at very low potentials. The developed sunset yellow sensor exhibited a high sensitivity of 4.16 µA µM-1 cm-2 and a nanomolar detection limit of 0.9 nM in the linear range 0.125-108.5 µM. Furthermore, experiments were conducted to affirm excellent stability, reproducibility, repeatability, and selectivity of proposed sensor. The practicality of sunset yellow determination using the developed sensor was analyzed in different varieties of food samples including jelly, soft drink, ice cream, and candy resulting in recovery in the range of 96.16%-102.56%.


Assuntos
Compostos Azo/análise , Técnicas Eletroquímicas/métodos , Corantes de Alimentos/análise , Nanopartículas Metálicas/química , Nanocompostos/química , Óxido de Alumínio/química , Cobalto/química , Grafite , Limite de Detecção , Modelos Lineares , Óxido de Magnésio/química , Níquel/química , Óxidos/química , Reprodutibilidade dos Testes
10.
Environ Sci Technol ; 56(2): 1341-1351, 2022 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-34964609

RESUMO

We introduce a new graphene oxide (GO)-based membrane architecture that hosts cobalt catalysts within its nanoscale pore walls. Such an architecture would not be possible with catalysts in nanoscale, the current benchmark, since they would block the pores or alter the pore structure. Therefore, we developed a new synthesis procedure to load cobalt in an atomically dispersed fashion, the theoretical limit in material downsizing. The use of vitamin C as a mild reducing agent was critical to load Co as dispersed atoms (Co1), preserving the well-stacked 2D structure of GO layers. With the addition of peroxymonosulfate (PMS), the Co1-GO membrane efficiently degraded 1,4-dioxane, a small, neutral pollutant that passes through nanopores in single-pass treatment. The observed 1,4-dioxane degradation kinetics were much faster (>640 times) than the kinetics in suspension and the highest among reported persulfate-based 1,4-dioxane destruction. The capability of the membrane to reject large organic molecules alleviated their effects on radical scavenging. Furthermore, the advanced oxidation also mitigated membrane fouling. The findings of this study present a critical advance toward developing catalytic membranes with which two distinctive and complementary processes, membrane filtration and advanced oxidation, can be combined into a single-step treatment.


Assuntos
Poluentes Ambientais , Grafite , Catálise , Cobalto/química
11.
Molecules ; 26(17)2021 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-34500638

RESUMO

The effect of humidity on sheep wool during irradiation by an accelerated electron beam was examined. Each of the samples with 10%, 53%, and 97% relative humidity (RH) absorbed a dose of 0, 109, and 257 kGy, respectively. After being freely kept in common laboratory conditions, the samples were subjected to batch Co(II) sorption experiments monitored with VIS spectrometry for different lapses from electron beam exposure. Along with the sorption, FTIR spectral analysis of the wool samples was conducted for cysteic acid and cystine monoxide, and later, the examination was completed, with pH measuring 0.05 molar KCl extract from the wool samples. Besides a relationship to the absorbed dose and lapse, the sorptivity results showed considerable dependence on wool humidity under exposure. When humidity was deficient (10% RH), the sorptivity was lower due to limited transformation of cystine monoxide to cysteic acid. The wool pre-conditioned at 53% RH, which is the humidity close to common environmental conditions, demonstrated the best Co(II) sorptivity in any case. This finding enables the elimination of pre-exposure wool conditioning in practice. Under excessive humidity of 97% RH and enough high dose of 257 kGy, radiolysis of water occurred, deteriorating the sorptivity. Each wool humidity, dose, and lapse showed a particular scenario. The time and humidity variations in the sorptivity for the non-irradiated sample were a little surprising; despite the absence of electron irradiation, relevant results indicated a strong sensitivity to pre-condition humidity and lapse from the start of the monitoring.


Assuntos
Cobalto/química , Íons/química , Ovinos/metabolismo , Lã/química , Adsorção/fisiologia , Animais , Cistina/química , Elétrons , Umidade , Água/química
12.
Proc Natl Acad Sci U S A ; 118(16)2021 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-33850014

RESUMO

Enzymes that bear a nonnative or artificially introduced metal center can engender novel reactivity and enable new spectroscopic and structural studies. In the case of metal-organic cofactors, such as metalloporphyrins, no general methods exist to build and incorporate new-to-nature cofactor analogs in vivo. We report here that a common laboratory strain, Escherichia coli BL21(DE3), biosynthesizes cobalt protoporphyrin IX (CoPPIX) under iron-limited, cobalt-rich growth conditions. In supplemented minimal media containing CoCl2, the metabolically produced CoPPIX is directly incorporated into multiple hemoproteins in place of native heme b (FePPIX). Five cobalt-substituted proteins were successfully expressed with this new-to-nature cobalt porphyrin cofactor: myoglobin H64V V68A, dye decolorizing peroxidase, aldoxime dehydratase, cytochrome P450 119, and catalase. We show conclusively that these proteins incorporate CoPPIX, with the CoPPIX making up at least 95% of the total porphyrin content. In cases in which the native metal ligand is a sulfur or nitrogen, spectroscopic parameters are consistent with retention of native metal ligands. This method is an improvement on previous approaches with respect to both yield and ease-of-implementation. Significantly, this method overcomes a long-standing challenge to incorporate nonnatural cofactors through de novo biosynthesis. By utilizing a ubiquitous laboratory strain, this process will facilitate spectroscopic studies and the development of enzymes for CoPPIX-mediated biocatalysis.


Assuntos
Metaloporfirinas/química , Porfirinas/biossíntese , Porfirinas/química , Biocatálise , Cobalto/química , Cobalto/metabolismo , Escherichia coli/metabolismo , Proteínas de Escherichia coli/metabolismo , Heme/metabolismo , Ferro , Metais/química , Mioglobina/química , Protoporfirinas/biossíntese , Protoporfirinas/química
13.
Acc Chem Res ; 54(8): 2003-2013, 2021 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-33797888

RESUMO

Metals are partners for an estimated one-third of the proteome and vary in complexity from mononuclear centers to organometallic cofactors. Vitamin B12 or cobalamin represents the epitome of this complexity and is the product of an assembly line comprising some 30 enzymes. Unable to biosynthesize cobalamin, mammals rely on dietary provision of this essential cofactor, which is needed by just two enzymes, one each in the cytoplasm (methionine synthase) and the mitochondrion (methylmalonyl-CoA mutase). Brilliant clinical genetics studies on patients with inborn errors of cobalamin metabolism spanning several decades had identified at least seven genetic loci in addition to the two encoding B12 enzymes. While cells are known to house a cadre of chaperones dedicated to metal trafficking pathways that contain metal reactivity and confer targeting specificity, the seemingly supernumerary chaperones in the B12 pathway had raised obvious questions as to the rationale for their existence.With the discovery of the genes underlying cobalamin disorders, our laboratory has been at the forefront of ascribing functions to B12 chaperones and elucidating the intricate redox-linked coordination chemistry and protein-linked cofactor conformational dynamics that orchestrate the processing and translocation of cargo along the trafficking pathway. These studies have uncovered novel chemistry that exploits the innate chemical versatility of alkylcobalamins, i.e., the ability to form and dismantle the cobalt-carbon bond using homolytic or heterolytic chemistry. In addition, they have revealed the practical utility of the dimethylbenzimidazole tail, an appendage unique to cobalamins and absent in the structural cousins, porphyrin, chlorin, and corphin, as an instrument for facilitating cofactor transfer between active sites.In this Account, we navigate the chemistry of the B12 trafficking pathway from its point of entry into cells, through lysosomes, and into the cytoplasm, where incoming cobalamin derivatives with a diversity of upper ligands are denuded by the ß-ligand transferase activity of CblC to the common cob(II)alamin intermediate. The broad reaction and lax substrate specificity of CblC also enables conversion of cyanocobalamin (technically, vitamin B12, i.e., the form of the cofactor in one-a-day supplements), to cob(II)alamin. CblD then hitches up with CblC via a unique Co-sulfur bond to cob(II)alamin at a bifurcation point, leading to the cytoplasmic methylcobalamin or mitochondrial 5'-deoxyadenosylcobalamin branch. Mutations at loci upstream of the junction point typically affect both branches, leading to homocystinuria and methylmalonic aciduria, whereas mutations in downstream loci lead to one or the other disease. Elucidation of the biochemical penalties associated with individual mutations is providing molecular insights into the clinical data and, in some instances, identifying which cobalamin derivative(s) might be therapeutically beneficial.Our studies on B12 trafficking are revealing strategies for cofactor sequestration and mobilization from low- to high-affinity and low- to high-coordination-number sites, which in turn are regulated by protein dynamics that constructs ergonomic cofactor binding pockets. While these B12 lessons might be broadly relevant to other metal trafficking pathways, much remains to be learned. This Account concludes by identifying some of the major gaps and challenges that are needed to complete our understanding of B12 trafficking.


Assuntos
Complexos de Coordenação/química , Vitamina B 12/metabolismo , Cobalto/química , Cobamidas/química , Humanos , Lisossomos/metabolismo , Metilmalonil-CoA Mutase/química , Metilmalonil-CoA Mutase/metabolismo , Metiltransferases/química , Metiltransferases/metabolismo , Mitocôndrias/metabolismo , Oxirredução , Estrutura Terciária de Proteína , Vitamina B 12/análogos & derivados , Vitamina B 12/química
14.
Bioprocess Biosyst Eng ; 44(7): 1423-1432, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-33709297

RESUMO

Cobalt oxide nanoparticles were prepared via green chemistry route and fully characterized by Field Emission Scanning Electron Microscope (FESEM), Energy-dispersive X-ray spectroscopy (EDAX), X-ray diffraction (XRD), High-resolution transmission electron microscopy (HRTEM) and Transmission electron microscopy (TEM) analyses; the CoO and Co3O4 nanoparticles, in sheet-shaped cobalt oxide form, ensued simultaneously in one step. The varying concentrations of NPs were analyzed via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) test on the cancer cell line (U87) which revealed that with increasing concentration of cobalt oxide nanoparticles, the survival rate of U87 tumor cells decreases; IC50 of nanoparticles being ~ 55 µg/ml-1.


Assuntos
Cobalto/química , Química Verde/métodos , Nanopartículas Metálicas/química , Nanotecnologia/métodos , Óxidos/química , Antibacterianos/química , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Humanos , Concentração de Íons de Hidrogênio , Concentração Inibidora 50 , Magnetismo , Testes de Sensibilidade Microbiana , Microscopia Eletrônica de Transmissão , Nanomedicina/métodos , Extratos Vegetais , Rosmarinus , Solubilidade , Espectroscopia de Infravermelho com Transformada de Fourier , Tensoativos , Temperatura , Sais de Tetrazólio/química , Tiazóis/química , Difração de Raios X
15.
J Fluoresc ; 31(3): 763-774, 2021 May.
Artigo em Inglês | MEDLINE | ID: mdl-33655457

RESUMO

Carbon quantum dots (CQD) as the result of their exceptional physical and chemical properties show tremendous potential in various field of applications like cell imaging and doping of CQDs with elements like nitrogen and phosphorous increase its fluorescence property. Herein, we have synthesized fluorescent nitrogen and phosphorous codoped carbon quantum dots (NPCQDs) via a one-pot hydrothermal method. Sesame oil, L-Aspartic acid, and phosphoric acid were used as carbon, nitrogen, and phosphorous sources, respectively. UV-Vis spectrophotometer, fluorescence spectrometer, Fourier transform infrared spectrometer (FTIR), X-ray diffraction spectrometer (XRD), field emission scanning microscopy (FESEM), and transmission electron microscopy (TEM) were employed to characterize the synthesized fluorescent NPCQDs. The as-synthesized NPCQDs with a particle size of 4.7 nm possess excellent water solubility, high fluorescence with high quantum yield (46%), high ionic stability, and resistance to photobleaching. MTT assay indicated the biocompatibility of NPCQDs and it was used for multicolor live-cell imaging. Besides, the NPCQDs show an effective probe of iron ions (Fe3+) in an aqueous solution with a high degree of sensitivity and selectivity. The DPPH assay showed its good antioxidant activity.


Assuntos
Carbono/química , Cobalto/química , Ferro/análise , Imagem Molecular/métodos , Nitrogênio/química , Fósforo/química , Pontos Quânticos/química , Antioxidantes/química , Antioxidantes/farmacologia , Sobrevivência Celular , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/química
16.
Molecules ; 26(4)2021 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-33579044

RESUMO

The cobalt-seleno-based coordination complex, [Co{(SePiPr2)2N}2], is reported with respect to its catalytic activity in oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solutions. An overpotential of 320 and 630 mV was required to achieve 10 mA cm-2 for OER and HER, respectively. The overpotential for OER of this CoSe4-containing complex is one of the lowest that has been observed until now for molecular cobalt(II) systems, under the reported conditions. In addition, this cobalt-seleno-based complex exhibits a high mass activity (14.15 A g-1) and a much higher turn-over frequency (TOF) value (0.032 s-1) at an overpotential of 300 mV. These observations confirm analogous ones already reported in the literature pertaining to the potential of molecular cobalt-seleno systems as efficient OER electrocatalysts.


Assuntos
Cobalto/química , Eletroquímica , Selênio/química , Água/química , Catálise , Modelos Moleculares
17.
Molecules ; 26(2)2021 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-33440778

RESUMO

Nitrogen-containing flame retardants have been extensively applied due to their low toxicity and smoke-suppression properties; however, their poor charring ability restricts their applications. Herein, a representative nitrogen-containing flame retardant, polyheptanazine, was investigated. Two novel, cost-effective phosphorus-doped polyheptazine (PCN) and cobalt-anchored PCN (Co@PCN) flame retardants were synthesized via a thermal condensation method. The X-ray photoelectron spectroscopy (XPS) results indicated effective doping of P into triazine. Then, flame-retardant particles were introduced into thermoplastic polyurethane (TPU) using a melt-blending approach. The introduction of 3 wt% PCN and Co@PCN could remarkably suppress peak heat release rate (pHRR) (48.5% and 40.0%), peak smoke production rate (pSPR) (25.5% and 21.8%), and increasing residues (10.18 wt%→17.04 wt% and 14.08 wt%). Improvements in charring stability and flame retardancy were ascribed to the formation of P-N bonds and P=N bonds in triazine rings, which promoted the retention of P in the condensed phase, which produced additional high-quality residues.


Assuntos
Compostos Aza/química , Retardadores de Chama , Heptanos/química , Poliuretanos/química , Cobalto/química , Retardadores de Chama/análise , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Fósforo/química , Pirólise , Temperatura
18.
Microsc Res Tech ; 84(2): 192-201, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33332709

RESUMO

The tunable cobalt oxide nanoparticles (CoONPs) are produced due to the phytochemicals present in Rhamnus virgata (RhV) leaf extract which functions as reducing and stabilization agents. The synthesis of CoONPs was confirmed using different analytical techniques: UV-Vis spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), dynamics light scatterings (DLS), Fourier-transform infrared spectroscopy (FTIR), energy dispersive X-ray, and Raman spectroscopy analyses. Furthermore, multiple biological activities were performed. Significant antifungal and antibacterial potentials have been reported. The in vitro cytotoxic assays of CoONPs revealed strong anticancer activity against human hepatoma HUH-7 (IC50 : 33.25 µg/ml) and hepatocellular carcinoma HepG2 (IC50 : 11.62 µg/ml) cancer cells. Dose-dependent cytotoxicity potency was confirmed against Leishmania tropica (KMH23 ); amastigotes (IC50 : 58.63 µg/ml) and promastigotes (IC50 : 32.64 µg/ml). The biocompatibility assay using red blood cells (RBCs; IC50 : 4,636 µg/ml) has confirmed the bio-safe nature of CoONPs. On the whole, results revealed nontoxic nature of RhV-CoONPs with promising biological potentials.


Assuntos
Antineoplásicos/farmacologia , Antiparasitários/farmacologia , Cobalto/química , Nanopartículas Metálicas/química , Óxidos/química , Extratos Vegetais/química , Folhas de Planta/química , Rhamnus/química , Linhagem Celular Tumoral , Humanos , Leishmania tropica/efeitos dos fármacos , Análise Espectral , Difração de Raios X
19.
Int J Biol Macromol ; 166: 190-199, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-33164774

RESUMO

Cold-adapted endo-ß-1,4-glucanases hold great potential for industrial processes requiring high activity at mild temperatures such as in food processing and extraction of bioactive compounds from plants. Here, we identified and explored the specificity, mode of action, kinetic behavior, molecular structure and biotechnological application of a novel endo-ß-1,4-glucanase (XacCel8) from the phytopathogen Xanthomonas citri subsp. citri. This enzyme belongs to an uncharacterized phylogenetic branch of the glycoside hydrolase family 8 (GH8) and specifically cleaves internal ß-1,4-linkages of cellulose and mixed-linkage ß-glucans releasing short cello-oligosaccharides ranging from cellobiose to cellohexaose. XacCel8 acts in near-neutral pHs and in a broad temperature range (10-50 °C), which are distinguishing features from conventional thermophilic ß-1,4-glucanases. Interestingly, XacCel8 was greatly stimulated by cobalt ions, which conferred higher conformational stability and boosted the enzyme turnover number. The potential application of XacCel8 was demonstrated in the caffeine extraction from guarana seeds, which improved the yield by 2.5 g/kg compared to the traditional hydroethanolic method (HEM), indicating to be an effective additive in this industrial process. Therefore, XacCel8 is a metal-stimulated and cold-adapted endo-ß-1,4-glucanase that could be applied in a diverse range of biotechnological processes under mild conditions such as caffeine extraction from guarana seeds.


Assuntos
Proteínas de Bactérias/metabolismo , Cafeína/química , Temperatura Baixa , Glucana 1,4-beta-Glucosidase/metabolismo , Sementes/química , Proteínas de Bactérias/química , Biocatálise , Cafeína/análise , Cobalto/química , Estabilidade Enzimática , Glucana 1,4-beta-Glucosidase/química , Paullinia/química , Xanthomonas/enzimologia
20.
ACS Appl Mater Interfaces ; 12(47): 52713-52720, 2020 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-33170623

RESUMO

Based on the signal amplification elements of planar VS2/AuNPs nanocomposites and CoFe2O4 nanozyme, we herein developed an electrochemical biosensor for sensitive kanamycin (Kana) quantification. A ratiometric sensing platform was presented by incorporating VS2/AuNPs nanocomposites as a support material with excellent conductivity and high specific surface area, as well as hairpin DNA (hDNA) with complementary hybridization of biotinylated Kana-aptamer. In addition, streptavidin-functionalized CoFe2O4 nanozyme with superior peroxidase-like catalytic activity were immobilized onto the aptasensor, hence the peroxidase-like catalytic reaction could yield amplified electrochemical signals. With the presence of Kana, the aptamer-biorecognition resulted in a quantitative decrease of nanozyme accumulation and an increase of methylene blue response. Under optimal conditions, the electrochemical signal ratio of the aptasensor revealed a linear relation along with the logarithmic concentration of Kana from 1 pM to 1 µM, with the limit of detection reaching to 0.5 pM. Moreover, this aptasensor exhibited excellent precision, as well as high repeatability, hence possessing potentials in real samples and for diverse targets detection by easy replacement of the matched aptamer.


Assuntos
Técnicas Biossensoriais/métodos , Canamicina/análise , Animais , Aptâmeros de Nucleotídeos/química , Cobalto/química , Técnicas Eletroquímicas , Compostos Férricos/química , Ouro/química , Limite de Detecção , Nanopartículas Metálicas/química , Leite/química , Nanoestruturas/química , Reprodutibilidade dos Testes , Compostos de Vanádio/química
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