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1.
J Agric Food Chem ; 67(35): 9942-9949, 2019 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-31403785

RESUMO

We develop an ultrasensitive T2-mediated immunosensor based on the coordination chemistry and Cu(I)-catalyzed 1,3-dipolar cycloaddition of azide andalkyne (CuAAC) and apply it for the detection of pesticide residues. We functionalize polyglutamic acid (PGA) on polystyrene to form a brush-like nanostructure that has a large loading capacity of Cu(II) through the coordination chemistry between PGA and Cu(II). Such a brush-like nanostructure could be used to chelate Cu(II) to modulate the CuAAC between azide-functionalized 1000 nm polystyrene (PS1000) and alkyne-functionalized 30 nm magnetic nanoparticles (MNP30), and the MNP30-PS1000 conjugate as a product of CuAAC can act as a magnetic probe in this T2-based immunosensor. This click chemistry and coordination chemistry-mediated immunosensor allows for an ultrasensitive detection for chlorpyrifos residue (0.022 ng/mL), a 58-fold enhancement compared with that of enzyme-linked immunosorbent assay (1.28 ng/mL), providing a promising platform for detection of trace small molecules.


Assuntos
Técnicas Biossensoriais/métodos , Clorpirifos/análise , Nanoestruturas/química , Resíduos de Praguicidas/análise , Alquinos/química , Azidas/química , Técnicas Biossensoriais/instrumentação , Quelantes/química , Química Click , Cobre/química , Água Potável/análise , Lagos/análise , Ácido Poliglutâmico/química , Sensibilidade e Especificidade , Poluentes da Água/análise
2.
Phys Chem Chem Phys ; 21(35): 19288-19297, 2019 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-31451821

RESUMO

This paper reports a facile, fast, and cost-effective method for the synthesis of three-dimensional (3D) porous AgNPs/Cu composites as SERS substrates for the super-sensitive and quantitative detection of food organic contaminations. Due to the 3D porous hotspot architecture and the strong plasmonic coupling between Ag and Cu, the porous AgNPs/Cu substrate achieves ultrasensitive detection of multiple analytes as low as 10-11 M (crystal violet, CV), 10-9 M (malachite green, MG), 10-11 M (acephate), and 10-9 M (thiram) even with a portable Raman device. Moreover, this 3D solid substrate has good signal uniformity (RSD < 11%) and superior stability (<14% signal loss), allowing for practical SERS detections. Importantly, by simply wiping the real sample surface using the substrate, it successfully detects CV and MG residues on crayfish, and the limit of detection (LOD) of CV and MG is determined to be 1.14 × 10-9 M and 0.94 × 10-7 M, respectively. Further, the substrate can also be applied to detect acephate on eggplant with a LOD of 1.41 × 10-9 M and thiram on an apple surface with a LOD of 1.04 × 10-7 M. Note that all these SERS detections on real samples have a broad dynamic concentration range and a good linear dependence. As a "proof of concept", multi-component detection on a real sample has also been demonstrated. This 3D solid substrate possesses excellent detection sensitivity, diversity, and accuracy, which allows rapid and reliable determination of toxic substances in foods.


Assuntos
Técnicas de Química Analítica/métodos , Análise de Alimentos/métodos , Contaminação de Alimentos/análise , Praguicidas/análise , Análise Espectral Raman , Animais , Técnicas de Química Analítica/economia , Cobre/química , Limite de Detecção , Nanopartículas Metálicas/química , Reprodutibilidade dos Testes , Prata/química
3.
Water Sci Technol ; 80(1): 98-108, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31461426

RESUMO

The sorption of Cu ions on pure fly ash-based geopolymer, fly ash-based geopolymer with Pb ions addition (modified) and zeolite NaX was studied. Taguchi's approach was applied to determine the impact of solute concentration (c), temperature (T), mixing time (t) and sorbent type (S) on the sorption of Cu ions onto different sorbents under batch conditions. Optimum experimental conditions and influence of controllable factors were determined using the larger-the-better approach. The influence in descending order is c > S > t > T, for both removal and loading. Also, the impact of sorbent type and solute concentration on the process equilibrium was examined. The equilibrium amount of Cu retained on the sorbents in equilibrium (qe) was as follows: pure geopolymer - 1.169 mmol g-1, modified geopolymer - 1.186 mmol g-1, and zeolite NaX - 1.695 mmol g-1. The experimental data were modelled using Jovanovic, Khan, Baudu, and Fritz-Schlünder isotherm models and their goodness of fit were compared. The Baudu isotherm model was the most useful in predicting the equilibrium of Cu sorption on pure and modified geopolymer. Goodness of fit of the selected isotherm models for the sorption of Cu ions on zeolite NaX was in the order: Fritz-Schlünder > Khan > Jovanovic > Baudu.


Assuntos
Cobre/química , Zeolitas , Adsorção , Concentração de Íons de Hidrogênio , Íons , Cinética , Modelos Químicos
4.
Water Sci Technol ; 80(1): 126-133, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31461429

RESUMO

This work is dedicated to the removal of free cyanide from aqueous solution through oxidation with hydrogen peroxide H2O2 catalyzed by copper oxide nanoparticles. Effects of initial molar ratio [H2O2]0/[CN-]0, catalyst dose, temperature, pH and the catalyst stability on cyanide removal have been investigated. The use of copper oxide has improved the reaction rate showing catalytic activity. The cyanide removal efficiency was increased from 60% to 94% by increasing in the dose of catalyst from 0.5 g/L to 5.0 g/L. Increasing the temperature from 20 °C to 35 °C promotes cyanide removal and the four successive times re-use of catalyst shows good stability. Kinetics of cyanide removal was found to be of pseudo-first-order with respect to cyanide. The rate constants have been determined.


Assuntos
Cobre/química , Cianetos/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Catálise , Peróxido de Hidrogênio/química , Oxirredução
5.
Water Sci Technol ; 80(1): 164-172, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31461433

RESUMO

The purpose of this study was to investigate the effect of Cu(II) on the adsorption performance and mechanism of tetracycline (TC) adsorption by natural zeolite (NZ) in aqueous solution. Low levels of Cu(II) (<0.01 mmol/L) enhanced the extent of TC adsorption from ∼0.4 mg/g (in the absence of Cu(II)) to ∼0.5 mg/g (with 0.01 mmol/L Cu(II)), resulting in 99% removal of the total TC content. The TC adsorption gradually decreased with increase in the initial pH, but the coexistence of Cu(II) lowered the extent of decrease. The adsorption process was better simulated by the pseudo-second-order kinetics model, but the isotherm model that was more fitting changed from the Langmuir to the Freundlich model as Cu(II) increased, indicating the coexistence of Cu(II) and TC altered the adsorption mechanisms. However, the residual TC in solution increased from 0 to ∼6 mg/L as the concentration of Cu(II) increased from 0 to 1 mmol/L, suggesting a competition between TC and Cu(II) for the adsorption sites in NZ. Fourier transform infrared spectroscopy analysis showed that the functional groups on the surface of NZ changed after the adsorption of TC, suggesting that complex reactions had occurred on the surface of the adsorbent.


Assuntos
Cobre/química , Tetraciclina/química , Poluentes Químicos da Água/química , Adsorção , Concentração de Íons de Hidrogênio , Cinética , Espectroscopia de Infravermelho com Transformada de Fourier , Eliminação de Resíduos Líquidos , Zeolitas/química
6.
Water Sci Technol ; 80(1): 184-190, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31461435

RESUMO

An electrochemical flow cell was introduced into the electrochemical Fenton-type process using a Cu(I)/HOCl system. The effects of the current density and the initial cupric ion (Cu2+) concentration on the process performance were discussed. The current efficiency of the process improved from 6.1% for an electrolytic tank system to 33% for the electrochemical flow cell system at a current density of 5.0 mA/cm2 and an initial Cu2+ concentration of 1.0 mM. The current efficiency increased to 58% for Cu2+ concentrations of 2.0 mM and beyond. The cathodic reduction of Cu2+ to the cuprous ion (Cu+) emerged as the rate-determining step in comparison to the anodic production of free chlorine. The introduction of the electrochemical flow cell enhanced the cathodic production of Cu+ by reinforcing the mass transfer of the Cu2+ to the cathode, and the detachment of micro bubbles generated electrochemically at the cathode surface. A decrease in the current density and an increase in the initial Cu2+ concentration also improved the current efficiency by promoting the cathodic production of Cu+. This involved the prevention of the cathodic reduction of protons to hydrogen gas and the elevation of the electrode potential of the cathodic reaction from Cu2+ to Cu+.


Assuntos
Eliminação de Resíduos Líquidos/métodos , Cobre/química , Eletrodos , Oxirredução
7.
Life Sci ; 234: 116758, 2019 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-31421083

RESUMO

In this work, fluorescent copper oxide nanoparticles (CuO NPs) were green synthesized using viable cells, cell lysate supernatant (CLS) and protein extracts of luminescent Vibrio sp. VLC. Biogenic CuO NPs were then characterized by XRD, FTIR, UV/Vis spectroscopy, TEM, DLS, and PL spectroscopy. Results showed that CLS method was more efficient for CuO NPs production, therefore CuO NPs synthesized by this method from copper sulfate (CuO NPs-1) and/or copper nitrate (CuO NPs-2) were used for further studies. The crystallite size of polydispersed CuO NPs-1 and CuO NPs-2 were about 8.83 and 8.77 nm, respectively indicating their suitability for biological applications. Antibacterial activity of CuO NPs was determined using broth microdilution, well diffusion agar, and time-kill curves methods. Both CuO NP-1 and CuO NP-2 inhibited bacterial growth at the minimum inhibitory concentration (MIC) of 625 mg/L except St. mutants (MIC = 1250 mg/L). Emission of fluorescent light from the surface of NPs was increased when exposed to Cd2+, As2+ and Hg2+ ions but decreased by Pb2+ ions. Results showed that CuO NP-1 had anticancer properties against KYSE30 esophageal cancer cell line (IC50 = 13.96 mg/L) while no higher cytotoxic effects were observed on Human Dermal Fibroblasts (HDF) (IC50 = 48.88 mg/L).


Assuntos
Antibacterianos/farmacologia , Antineoplásicos/farmacologia , Cobre/farmacologia , Neoplasias Esofágicas/tratamento farmacológico , Corantes Fluorescentes/química , Metais Pesados/análise , Nanopartículas/química , Antibacterianos/química , Antineoplásicos/química , Bactérias/efeitos dos fármacos , Infecções Bacterianas/tratamento farmacológico , Linhagem Celular Tumoral , Cobre/química , Química Verde/métodos , Humanos , Espectrometria de Fluorescência/métodos , Vibrio/química
8.
Chem Biol Interact ; 311: 108789, 2019 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-31401089

RESUMO

The cytotoxicity of a dinuclear imine-copper (II) complex 2, and its analogous mononuclear complex 1, toward different melanoma cells, particularly human SKMEL-05 and SKMEL-147, was investigated. Complex 2, a tyrosinase mimic, showed much higher activity in comparison to complex 1, and its reactivity was verified to be remarkably activated by UVB-light, while the mononuclear compound showed a small or negligible effect. Further, a significant dependence on the melanin content in the tumor cells, both from intrinsic pigmentation or stimulated by irradiation, was observed in the case of complex 2. Similar tests with keratinocytes and melanocytes indicated a much lower sensitivity to both copper (II) complexes, even after exposition to UV light. Clonogenic assays attested that the fractions of melanoma cells survival were much lower under treatment with complex 2 compared to complex 1, both with or without previous irradiation of the cells. The process also involves generation of reactive oxygen species (ROS), as verified by EPR spectroscopy, and by using fluorescence indicators. Autophagic assays indicated a remarkable formation of cytoplasmic vacuoles in melanomas treated with complex 2, while this effect was not observed in similar treatment with complex 1. Monitoring of specific protein LC3 corroborated the simultaneous occurrence of autophagy. A balance interplay between different modes of cell death, apoptosis and autophagy, occurs when melanomas were treated with the dinuclear complex 2, in contrast to the mononuclear complex 1. These results pointed out to different mechanisms of action of such complexes, depending on its nuclearity.


Assuntos
Complexos de Coordenação/química , Cobre/química , Iminas/química , Monofenol Mono-Oxigenase/metabolismo , Animais , Autofagia/efeitos dos fármacos , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos da radiação , Complexos de Coordenação/metabolismo , Complexos de Coordenação/farmacologia , Espectroscopia de Ressonância de Spin Eletrônica , Pontos de Checagem da Fase G1 do Ciclo Celular/efeitos dos fármacos , Pontos de Checagem da Fase G1 do Ciclo Celular/efeitos da radiação , Humanos , Melaninas/metabolismo , Melanoma/metabolismo , Melanoma/patologia , Camundongos , Mitocôndrias/efeitos dos fármacos , Mitocôndrias/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Tubulina (Proteína)/metabolismo , Raios Ultravioleta
9.
Chem Commun (Camb) ; 55(60): 8880-8883, 2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31321399

RESUMO

We developed an artificial hydrolase based on the symmetrical Pizza6 ß-propeller protein for the metal-free hydrolysis of 4-nitrophenyl acetate and butyrate. Through site-specific mutagenesis and crystallisation studies, the catalytic mechanism was investigated and found to be dependent on a threonine-histidine dyad. The mutant with additional histidine residues generated the highest kcat values, forming a His-His-Thr triad and matched previously reported metalloenzymes. The highly symmetrical ß-propeller artificial enzymes and their protein-metal complexes have potential to be utilised in bioinorganic and supramolecular chemistry, as well as being developed further into 2D/3D catalytic materials.


Assuntos
Hidrolases/química , Sequência de Aminoácidos , Ácido Aspártico/química , Ácido Aspártico/genética , Butiratos/química , Catálise , Cobre/química , Histidina/química , Histidina/genética , Hidrolases/genética , Hidrólise , Cinética , Mutagênese Sítio-Dirigida , Nitrofenóis/química , Engenharia de Proteínas/métodos , Estrutura Terciária de Proteína , Treonina/química , Zinco/química
10.
Ceska Slov Farm ; 68(2): 69-77, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31331176

RESUMO

Currently, the method of external ionic gelation for the preparation of alginate particles is successfully used not only in the field of pharmacy and medicine, but also especially in the field of biotechnology. Therefore, the preparation of alginate particles and their subsequent evaluation using principal component analysis was the key task of our experiment. To optimize this method, we focused on the evaluation of the effect of formulation (the polymer concentration, the hardening solution concentration) and process parameters (the outer diameter of the injection needle) on the properties of the resulting beads (yield, sphericity factor, equivalent diameter and swelling capacity at pH 6). Using multivariate data analysis, the major influence on the resulting properties of the prepared particles was confirmed only in sodium alginate concentration. Obtained results verified the reliable and safe potential of the external ionic gelation for preparation alginate-based particulate dosage forms.


Assuntos
Alginatos/química , Cobre/química , Polímeros , Análise de Componente Principal
11.
Top Curr Chem (Cham) ; 377(4): 21, 2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31332546

RESUMO

The present review highlights the most important recent contributions toward the synthesis of functionalized fused heteroaromatic rings via intramolecular C-H activation mediated or catalyzed by transition metals. This type of reaction constitutes a versatile strategy to obtain a great variety of fused heterocyclic systems through the formation of carbon-carbon (C-C) and C-heteroatom bonds from direct coupling between two adjacent C-H bonds or C-H/H-X bonds. The  revision is focused on the synthesis of fused heterocycles through two chemical processes: (1) metal-catalyzed intramolecular oxidative C-H activation, and (2) intramolecular C-H activation mediated by metallic Lewis acids.


Assuntos
Cobre/química , Compostos Heterocíclicos/síntese química , Paládio/química , Catálise , Compostos Heterocíclicos/química , Estrutura Molecular , Elementos de Transição
12.
Bioresour Technol ; 291: 121868, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31357045

RESUMO

To clarify the adsorption behaviors of typical heavy metals onto sludge extracellular polymeric substances (EPS), the adsorption capacities and mechanisms, as well as the contributions of the different EPS components (proteins, humic acids and polysaccharides), to the adsorption of Zn2+, Cu2+ and Cd2+ were separately explored. Overall, proteins exhibited a relatively high adsorption capacity for the three metals ions, followed by humic acid, whereas least for polysaccharides. The adsorption of Cu2+ and Cd2+ onto proteins, humic acid and polysaccharides fit well to the Freundlich isotherm, whereas Langmuir model was the best fit for Zn2+ bindings onto polysaccharides/humic acid. The binding of Cu2+, Zn2+ and Cd2+ onto the three EPS components was exothermically favorable, and significant electrostatic interactions were observed for the heavy metals sorption onto humic acid and proteins. In addition, the effect of metal ions sorption on the spectrum of the proteins, polysaccharides and humic acid was also explored.


Assuntos
Cádmio/química , Cobre/química , Substâncias Húmicas , Polissacarídeos/química , Proteínas/metabolismo , Esgotos , Zinco/química , Adsorção , Cádmio/metabolismo , Cobre/metabolismo , Proteínas/química , Esgotos/química , Zinco/metabolismo
13.
Inorg Chem ; 58(15): 9773-9784, 2019 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-31318533

RESUMO

In recent years, transition metal complexes have been developed for catalytical degradation of a phosphate ester bond, particularly in RNA and DNA; however, less consideration has been given for development of complexes for the degradation of a phosphorothioate bond, as they are the foremost used pesticides in the environment and are toxic to human beings. In this context, we have developed copper complexes of benzimidazolium based ligands for catalytical degradation of a series of organophosphates (parathion, paraoxon, methyl-parathion) at ambient conditions. The copper complexes (assigned as N1-N3) were characterized using single X-ray crystallography which revealed that all three complexes are mononuclear and distorted square planner in geometry. Further, the solution state studies of the prepared complexes were carried out using UV-visible absorption, fluorescence spectroscopy, and cyclic voltametry. The complexes N1 and N2 have benzimidazolium ionic liquid as base attached with two 2-mercapto-benzimidazole pods, whereas complex N3 contains a nonionic ligand. The synthesized copper complexes were evaluated for their catalytic activity for degradation of organophosphates. It is interesting that the complex containing the ionic ligand efficiently degrades phosphorothioate pesticides, whereas complex N3 was not found to be appropriate for degradation due to a weaker conversion rate. The organophosphate degradation studies were monitored by recording absorbance spectra of parathion in the presence of catalyst, i.e., copper complexes with respect to time. The parathion was hydrolyzed into para-nitrophenol and diethyl thiophosphate. Moreover, to analyze the inhibition activity of the pesticides toward acetylcholine esterase enzyme in the presence of prepared metal complexes, Ellman's assay was performed and revealed that, within 20 min, the inhibition of acetylcholine esterase enzyme decreases by up to 13%.


Assuntos
Acetilcolina/metabolismo , Esterases/metabolismo , Estruturas Metalorgânicas/química , Praguicidas/química , Praguicidas/toxicidade , Fosfatos/química , Acetilcolina/análise , Benzimidazóis/química , Catálise , Cobre/química , Cristalografia por Raios X , Esterases/análise , Estruturas Metalorgânicas/síntese química , Modelos Moleculares , Estrutura Molecular , Fosfatos/toxicidade
14.
Bioresour Technol ; 291: 121818, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31344637

RESUMO

A novel mesoporous biochar (PBC) was facilely prepared from Medulla tetrapanacis. PBC exhibited high efficiency for the sorption of Cu2+ (458.72 mg/g) and Pb2+ (1031.23 mg/g) ions, and these values were higher than that of reported literatures. In the multi-metal system, the maximum sorption capacity for Cu2+, Pb2+, Cr3+, and Fe3+ were 430.88 mg/g, 701.63 mg/g, 696.67 mg/g, and 697.01 mg/g, respectively, and the removal efficiencies of those ions were more than 80% at a metal ion concentration of 200 mg/L. Furthermore, the PBC was effective for the treatment of industrial effluent wastewater. The ash content (45.46%) of the PBC was higher than that of most other biochar derived from lignocellulosic biomass. Complexation, precipitation, π-π interactions, ion exchange, and physical sorption were the main sorption mechanisms. Overall, PBC is an inexpensive product, which is simply synthesized and an excellent adsorbent for heavy metal ion removal.


Assuntos
Carvão Vegetal/química , Cobre/química , Chumbo/química , Adsorção , Biomassa , Cátions Bivalentes/química , Troca Iônica
15.
J Photochem Photobiol B ; 197: 111556, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31326842

RESUMO

Facile green synthesis of copper nanoparticles from different biological procedures has been indicated, but among all, biosynthesis of copper nanoparticles from medicinal plants is considered as the most suitable method. The use of medicinal plant material increases the therapeutical effects of copper nanoparticles. The aim of this study was green synthesis of copper nanoparticles from aqueous extract of Falcaria vulgaris leaf (CuNPs) and assessment of their cytotoxicity, antioxidant, antifungal, antibacterial, and cutaneous wound healing properties. These nanoparticles were characterized by X-ray diffraction (XRD), fourier-transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM) analysis. The synthesized CuNPs had great cell viability dose-dependently (Investigating the effect of the CuNPs on human umbilical vein endothelial cell (HUVEC) line) and indicated this method was nontoxic. Also, 2,2-diphenyl-1-picrylhydrazyl (DPPH) test was done to assess the antioxidant activities, which indicated similar antioxidant potentials for CuNPs and butylated hydroxytoluene. In part of cutaneous wound healing property of CuNPs, after creating the cutaneous wound, the rats were randomly divided into six groups: treatment with 0.2% CuNPs ointment, treatment with 0.2% CuSO4 ointment, treatment with 0.2% F. vulgaris ointment, treatment with 3% tetracycline ointment, treatment with Eucerin basal ointment, and untreated control. These groups were treated for 10 days. Treatment with CuNPs ointment remarkably increased (p ≤ .01) the wound contracture, vessel, hexosamine, hydroxyl proline, hexuronic acid, fibrocyte, and fibrocytes/fibroblast rate and substantially reduced (p ≤ .01) the wound area, total cells, neutrophil, and lymphocyte compared to other groups. In antibacterial and antifungal parts of this research, the concentration of CuNPs with minimum dilution and no turbidity was considered minimum inhibitory concentration (MIC). To determine minimum fungicidal concentration (MFC) and minimum bactericidal concentration (MBC), 60 µL MIC and three preceding chambers were cultured on Sabouraud Dextrose Agar and Muller Hinton Agar, respectively. The minimum concentration with no fungal and bacterial growth were considered MFC and MBC, respectively. CuNPs inhibited the growth of all fungi at 2-4 mg/mL concentrations and removed them at 4-8 mg/mL concentrations (p ≤ .01). In case of antibacterial effects of CuNPs, they inhibited the growth of all bacteria at 2-8 mg/mL concentrations and removed them at 4-16 mg/mL concentrations (p ≤ .01). The results of XRD, FT-IR, UV, TEM, and FE-SEM confirm that the aqueous extract of F. vulgaris leaf can be used to yield copper nanoparticles with notable amount of antioxidant, antifungal, antibacterial, and cutaneous wound healing potentials without any cytotoxicity. Further clinical trials are necessary for confirmation these therapeutical effects of CuNPs in human.


Assuntos
Apiaceae/química , Cobre/química , Nanopartículas Metálicas/química , Extratos Vegetais/química , Animais , Antibacterianos/síntese química , Antibacterianos/química , Antibacterianos/farmacologia , Antifúngicos/síntese química , Antifúngicos/química , Antifúngicos/farmacologia , Antioxidantes/química , Apiaceae/metabolismo , Candida/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacos , Química Verde , Células Endoteliais da Veia Umbilical Humana , Humanos , Masculino , Nanopartículas Metálicas/toxicidade , Testes de Sensibilidade Microbiana , Folhas de Planta/química , Folhas de Planta/metabolismo , Ratos , Pele/efeitos dos fármacos , Pele/patologia , Cicatrização/efeitos dos fármacos
16.
Talanta ; 202: 279-284, 2019 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-31171183

RESUMO

Microcystin-LR (MC-LR) is a potent hepatotoxin that is often associated with blooms of cyanobacteria. The analysis of trace MC-LR plays important role in environmental and health fields. Herein, we developed a low-cost and enzyme-free detection method of MC-LR by using hairpin DNA-templated copper nanoclusters (hpDNA-CuNCs) as fluorescent probe. The hpDNA-template was designed and fabricated by a MC-LR aptamer loop and a double strand stem, which can specifically recognize target MC-LR with strong affinity. The AT-rich and complementary double strand stem serves as a template for the formation of CuNCs. The formed fluorescent sensing probe of hpDNA-CuNCs exhibits maximum emission wavelength at 575 nm. Upon the addition of target MC-LR into the hpDNA-CuNCs, we observed fluorescence was quenched considerably due to the high affinity between MC-LR and hpDNA aptamer strand loop, which indicated a conformational change of hairpin probe from the stem-loop DNA structure to single-stranded DNA. Then, the change of fluorescence intensity can be used to monitor the concentration of MC-LR from 0.005 to 1200 µg L-1 with a detection limit of 0.003 ng L-1. Compared with the previous reports, this method does not require complex DNA sequence design, fluorescence dye label and sophisticated experimental techniques. Moreover, the target MC-LR in real water samples has been detected.


Assuntos
Técnicas Biossensoriais , Cobre/química , DNA/química , Fluorescência , Corantes Fluorescentes/química , Nanopartículas Metálicas/química , Microcistinas/análise , Poluentes Químicos da Água/análise , Corantes Fluorescentes/síntese química , Espectrometria de Fluorescência
17.
Chem Commun (Camb) ; 55(60): 8860-8863, 2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31219109

RESUMO

We report the first dual-responsive 19F MRI and fluorescence imaging probe for cellular hypoxia. The Cu2+-based probe exhibits no 19F MR signal and reduced fluorescence signal due to paramagnetic quenching; however, the probe turns-on in both modes following reduction to Cu+. This bimodal agent can differentiate hypoxic and normoxic cells in both modalities.


Assuntos
Hipóxia Celular/fisiologia , Complexos de Coordenação/química , Fluoresceínas/química , Corantes Fluorescentes/química , Complexos de Coordenação/síntese química , Complexos de Coordenação/toxicidade , Cobre/química , Fluoresceínas/síntese química , Fluoresceínas/toxicidade , Fluorescência , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/toxicidade , Flúor , Imagem por Ressonância Magnética de Flúor-19/métodos , Células HeLa , Humanos , Concentração de Íons de Hidrogênio , Microscopia de Fluorescência/métodos
18.
Anal Bioanal Chem ; 411(20): 5277-5285, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31161325

RESUMO

Rapid, highly sensitive detection of tau protein and other neurodegenerative biomarkers remains a significant hurdle for diagnostic tests for Alzheimer's disease. In this work, we developed a novel tyrosinase (TYR)-induced tau aptamer-tau-tau antibody (anti-tau) sandwich fluorescence immunoassay to detect tau protein that used dopamine (DA)-functionalized CuInS2/ZnS quantum dots as the fluorophore. CuInS2/ZnS core/shell quantum dots with high luminescence, low toxicity, and excellent biocompatibility were successfully fabricated and decorated with DA through amide conjugation. Meanwhile, TYR was conjugated with anti-tau by a click reaction. When DA-functionalized CuInS2/ZnS quantum dots were added to the sandwich system, TYR catalyzed the transformation of DA to dopamine quinone, which acted as an effective electron acceptor and triggered fluorescence quenching. The fluorescence intensity of the immunoassay based on DA-functionalized CuInS2/ZnS quantum dots shows good performance in terms of linearity with the logarithm of tau protein concentration, with a linear concentration range from 10 pM to 200 nM. This work is the first to use a TYR-induced fluorescence immunoassay for the rapid detection of tau protein, paving a new way for the detection of disease biomarkers. Graphical abstract.


Assuntos
Cobre/química , Imunofluorescência/métodos , Índio/química , Monofenol Mono-Oxigenase/química , Pontos Quânticos/química , Selênio/química , Sulfetos/química , Compostos de Zinco/química , Proteínas tau/análise , Cristalografia por Raios X , Dopamina/análogos & derivados , Dopamina/química , Microscopia Eletrônica de Transmissão , Análise Espectral/métodos
19.
Nat Commun ; 10(1): 2675, 2019 06 17.
Artigo em Inglês | MEDLINE | ID: mdl-31209220

RESUMO

Aerobic methane oxidation is catalyzed by particulate methane monooxygenase (pMMO), a copper-dependent, membrane metalloenzyme composed of subunits PmoA, PmoB, and PmoC. Characterization of the copper active site has been limited by challenges in spectroscopic analysis stemming from the presence of multiple copper binding sites, effects of detergent solubilization on activity and crystal structures, and the lack of a heterologous expression system. Here we utilize nanodiscs coupled with native top-down mass spectrometry (nTDMS) to determine the copper stoichiometry in each pMMO subunit and to detect post-translational modifications (PTMs). These results indicate the presence of a mononuclear copper center in both PmoB and PmoC. pMMO-nanodisc complexes with a higher stoichiometry of copper-bound PmoC exhibit increased activity, suggesting that the PmoC copper site plays a role in methane oxidation activity. These results provide key insights into the pMMO copper centers and demonstrate the ability of nTDMS to characterize complex membrane-bound metalloenzymes.


Assuntos
Proteínas de Bactérias/metabolismo , Espectrometria de Massas/métodos , Methylococcaceae/metabolismo , Modelos Moleculares , Oxigenases/metabolismo , Proteínas de Bactérias/química , Proteínas de Bactérias/ultraestrutura , Sítios de Ligação , Biocatálise , Domínio Catalítico , Cobre/química , Cobre/metabolismo , Microscopia Crioeletrônica , Metano/metabolismo , Metanol/metabolismo , Methylococcaceae/química , Methylococcaceae/ultraestrutura , Oxirredução , Oxigenases/química , Oxigenases/ultraestrutura , Processamento de Proteína Pós-Traducional
20.
Chem Commun (Camb) ; 55(54): 7752-7755, 2019 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-31204733

RESUMO

Metal-binding peptides are versatile building blocks in supramolecular chemistry. We recently reported a class of crystalline materials formed through a combination of coiled-coil peptide self-association and metal coordination. Here, we probe the serendipitously discovered metal binding motif that drives the assembly and apply these insights to exert rational control over structure and morphology in the materials.


Assuntos
Metaloproteínas/química , Motivos de Aminoácidos , Sequência de Aminoácidos , Cobre/química , Espectroscopia de Ressonância de Spin Eletrônica/métodos , Metaloproteínas/síntese química , Engenharia de Proteínas/métodos , Multimerização Proteica , Piridinas/química
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