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1.
Food Chem X ; 19: 100857, 2023 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-37780334

RESUMO

The present research is the first report on the application of Keggin-type phosphotungstic acid/polyvinylidene fluoride membrane. This compound as a simple, cost-effective and novel sorbent was used for the extraction and pre-concentration of two organophosphorus pesticides in real samples in the thin film solid-phase microextraction (TFME) method. TFME as one of the sub-branches of solid phase microextraction resolves the problems of SPME methods, including their limited absorption capacity. These extraction methods have a high surface-to-volume ratio, which improves their sensitivity compared to other geometries. Under optimal conditions, the limit of detections (LODs), the limit of quantifications (LOQs), and relative standard deviation (RSD) of this method varied in the ranges of 0.29-0.31 µg L-1, 0.96-1.0 µg L-1, and 3.9%-6.2%, respectively. This method showed a linear dynamic range (LDR) of 1.0-500 µg L-1 with a coefficient of determination (r2) above 0.9978. This promising method was used to analyze malathion and diazinon.

2.
Mikrochim Acta ; 189(11): 432, 2022 10 26.
Artigo em Inglês | MEDLINE | ID: mdl-36284019

RESUMO

The study focuses on the electrochemical deposition of copper benzene-1,4-dicarboxylate framework (Cu-BDC MOF) on the surface of a very cheap pencil graphite (PG) substrate for utilization as the sorbent in fiber solid-phase microextraction (SPME) of two chosen pesticides, including abamectin and amitraz for the first time. The extracted pesticides were quantified by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). The UV detector was set at 236 nm wavelength. Based on the optimized condition, the presented technique showed a good linear range (2-500 µg L-1 and 2-100 µg L-1), suitable limits of detections (LODs = 0.60 and 0.5 µg L-1), satisfactory enhancement factors (EFs = 128 and 105), good absolute recoveries (ARs% = 64% and 53%) and spiking recoveries in the range 87.4-110.0% for amitraz and abamectin, respectively. Intra- and inter-day relative standard deviations were found within the range 1.2-3.8% and 0.6-1.9%, respectively. The method was successfully employed for the quantification of the selected pesticides in strawberry juice, lemon juice, orange juice, tomato juice, and honey.


Assuntos
Grafite , Estruturas Metalorgânicas , Praguicidas , Microextração em Fase Sólida/métodos , Praguicidas/análise , Galvanoplastia , Cobre , Benzeno
3.
Nucleosides Nucleotides Nucleic Acids ; 40(12): 1125-1143, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34632961

RESUMO

Cyclooxygenase-2 (COX-2) is an inducible inflammatory enzyme, which produces prostanoids from arachidonic acid. COX-2 overexpression and over-activity can cause inflammation, tumorigenesis, and angiogenesis. Prostanoids are the main reason for the inflammation, and increase of mitogenesis by COX-2. So, any change such as mutations that can lead to COX-2 over-activity could ignite the tumor situations with increase of prostanoids production is one of its ways. The aim of this study was to check the effect of 166 missense mutations of COX-2 on protein features that can affect the COX-2 activity such as protein stability, fluctuation, 2D structure, and its binding affinity with the substrate by in silico methods, network modeling, and docking calculations, by which 44 of them shown to be deleterious. Among them, the S124I and S474F mutations can increase the stability of the protein. 11.36% of deleterious nsSNPs were part of the substrate-binding region among which the M508T, H337R, and V511G have the potential to affect the protein by 2D structure alteration. V511G can improve binding affinity and H337R showed a small decrease in the deformation overall energy that can represent a decrease in the stability of COX-2. Also, L517S showed a significant decrease in the binding power of COX-2/substrate but based on the anisotropic network modeling this mutation has a dual effect on COX-2 stability. These nsSNPs/mutations have the potential causing an increase or decrease of tumorigenesis because increasing of COX-2 stability and its binding affinity can lead to altering its activity.


Assuntos
Ciclo-Oxigenase 2/genética , Simulação de Acoplamento Molecular , Ciclo-Oxigenase 2/química , Ciclo-Oxigenase 2/metabolismo , Humanos , Mutação de Sentido Incorreto , Conformação Proteica , Estabilidade Proteica , Especificidade por Substrato
4.
J Chromatogr A ; 1656: 462550, 2021 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-34537664

RESUMO

In this work, hierarchical ZIF-8 coated anodized aluminum foil was prepared through in situ template-directed method without addition of any zinc salt. The hierarchical sorbent was synthesized by the formation of the final HZIF-8 on the previously created layered double oxide (LDO) template. The LDO template was created by calcining the firstly in situ prepared desired layered double hydroxide (LDH) precursor coated on the electrochemically anodized porous Al foil in an air atmosphere. The microextraction ability of the extracting device was studied through direct immersion thin film microextraction (DI-TFME). The extracted analytes were quantified by high-performance liquid chromatography equipped by UV detector (HPLC-UV). The present strategy was used for the simultaneous extraction and quantification of four selected chlorophenols (CPs) (as model analyte). The variables of the TFME were optimized using response surface methodology (Plackett-Burman and Box-Behnken design). Under the obtained optimum condition, the prepared film presented acceptable extraction properties including low limits of detection (0.03-0.22 µgL-1), good linear ranges (0.2-200 µgL-1, r2 > 0.9918) and satisfactory reproducibility (relative standard deviation, 3.6 < RSD < 5.8% for one film as inter- and intra-day RSD, 4.8 < RSD < 5.3% for film to film). Moreover, the obtained enrichment factors were in the range of 56-76. The kinetics and adsorption isotherm of the selected analytes adsorption to the prepared sorbent were also investigated. The maximum adsorption capacities of the selected analytes on the prepared sorbent were in the range of 26.4-80.1 mg g-1. The adsorption isotherm obeyed the Langmuir and Freundlich models. Moreover, the adsorption of the selected chlorophenols on the prepared film followed the pseudo-second-order kinetic model. Finally, the HZIF-8 film was utilized for the quantification of selected CPs in different types of water and wastewater samples. The results showed satisfactory relative recoveries (93-102%) and acceptable precisions (3.6 < RSD < 9.2%).


Assuntos
Clorofenóis , Nanoporos , Zeolitas , Alumínio , Cromatografia Líquida de Alta Pressão , Limite de Detecção , Óxidos , Reprodutibilidade dos Testes , Microextração em Fase Sólida , Zinco
5.
J Sep Sci ; 44(6): 1264-1272, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-33400826

RESUMO

Herein, we present a simple, cost-effective, and robust strategy for the in-situ preparation of Zn-Al layered double oxides-anodized aluminum thin film via a facile hydrothermal method, followed by calcination treatment of the Zn-Al layered double hydroxide in the air atmosphere. The in-situ prepared Zn-Al layered double oxide-anodized aluminum film was implemented as sorbent for thin film microextraction of four selected chlorophenols (4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol), followed by high-performance liquid chromatography-ultraviolet detection. The different variables of the thin film microextraction were screened via Plackett-Burman design and then optimized through Box-Behnken design. Under the optimum condition, the method showed good linear ranges (0.2-200 µg/L) with the coefficient of determinations higher than 0.9938. The calculated limit of detections were between 0.07 and 0.56 µg/L. Relative standard deviations of the method for determination of the analytes at 5 µg/L concentration level (n = 3) were ranged from 3.5 to 3.9% (as interday). The enrichment factors were between 39 and 58. This extraction method was demonstrated to be fast, efficient, and convenient. To study the capability of the developed method for real sample analysis, tap, well, river, and two types of wastewater samples were satisfactorily analyzed.

6.
J Chromatogr A ; 1626: 461358, 2020 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-32797837

RESUMO

In this study, the in-situ conversion of the synthesized Co-Al layered double hydroxide (Co-Al LDH) nanosheets to three dimensional hierarchical zeolitic imidazolate framework-67 (3D HZIF-67) was presented as a cost-effective, highly efficient, flexible and robust sorbent to carry out the microextraction process. In the first stage, the anodized aluminum foil was prepared electrochemically. Then, the Co-Al LDH precursor was constructed on the surface of the previously-prepared anodized Al foil applying in-situ formation approach. The procedure is followed by the conversion of the prepared Co-Al LDH film to 3D HZIF-67 film via a facile solvothermal method without adding cobalt salt. The in-situ prepared 3D HZIF-67-anodized Al was used for the thin film microextraction (TFME) of caffeine. The effective factors in TFME procedure were investigated and optimized through applying Central Composite Design (CCD). In the obtained optimal condition, the calibration curves for TFME-HPLC-UV of caffeine were linear in the range of 1-200 µg L-1 with the coefficient of determination (r2) higher than 0.9915. The limits of detection were 0.33 and 0.38 µg L-1, in water and urine matrices, respectively. Moreover, the enrichment factors (EFs) and absolute recoveries (%AR) were also calculated as 173-198 and 57.1%-65.3%, respectively. The inter-day relative standard deviations (RSDs) were evaluated as the method precision for 20 and 200 µg L-1 of spiked sample and were between 4.9-6.1%. The repeatability of the preparation step was investigated as batch-to-batch reproducibility and it was found to be 4.9%; as a result, the reproducibility of the presented film was approved. Finally, the proposed method was utilized to determine caffeine (as the model analyte) from different types of real samples including urine, coffee, beverage (Pepsi) and shampoo. The obtained recoveries (higher than 88%) confirmed the capability of the method for real sample analysis.


Assuntos
Alumínio/química , Cafeína/isolamento & purificação , Cromatografia Líquida de Alta Pressão/métodos , Cobalto/química , Hidróxidos/química , Imidazóis/química , Raios Ultravioleta , Zeolitas/química , Adsorção , Eletrodos , Limite de Detecção , Microscopia de Força Atômica , Porosidade , Reprodutibilidade dos Testes , Solventes/química , Propriedades de Superfície
7.
Artigo em Inglês | MEDLINE | ID: mdl-32248046

RESUMO

The present study is the first report of in-situ growth and application of nanorods-flower like Co3O4 nanosorbent coated on the anodized aluminum substrate for thin film microextraction (TFME) approach. The flower like Co3O4 was successfully fabricated by conversion of Co-Al layered double hydroxide (LDH) precursor to Co3O4 using the simple calcinations process. The cheap and available aluminum foil was electrochemically anodized and used as a porous substrate. Response surface methodology (RSM) was explored for optimization step. Different acidic drugs, including: paracetamol, ibuprofen, aspirin and diclofenac were extracted from biological fluids in order to investigate the capability of the prepared sorbent. The extracted analytes were then analyzed using high performance liquid chromatography-ultraviolet detection (HPLC-UV). Under the optimized conditions, the limits of detection were between 0.2 and 1.7 µg L-1 in different selected matrices. The obtained limits of quantification were also calculated to be between 0.8 and 5.1 µg L-1 in the selected matrices. In addition the enrichment factors were also in the range of 105-169. Batch-to-batch reproducibility at 100 µg L-1 concentration level was also evaluated to be lower than 5.2% (n = 3). Finally, the method was successfully used for analysis of these compounds in the biological fluids.


Assuntos
Ácidos/urina , Alumínio/química , Cobalto/química , Nanotubos/química , Óxidos/química , Acetaminofen/urina , Adsorção , Adulto , Aspirina/urina , Cromatografia Líquida de Alta Pressão , Diclofenaco/urina , Técnicas Eletroquímicas , Eletrodos , Feminino , Humanos , Hidróxidos/química , Ibuprofeno/urina , Limite de Detecção , Masculino , Reprodutibilidade dos Testes , Microextração em Fase Sólida , Propriedades de Superfície
8.
Talanta ; 211: 120759, 2020 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-32070564

RESUMO

Allopurinol (ALO) is a radical scavenging clinical drug, a drug in the treatment of gout, an inhibitor of xanthine oxidase and an effective agent for anti-cancer purposes. The xanthine oxidase is thus essential, and the amount of ALO needs to be controlled more strictly. In this study, a new electrochemical sensor based on magnetite graphene oxide/ordered mesoporous carbon (Fe3O4@GO/OMC) hybrid was prepared and characterized. The results showed sphere shape Fe3O4 nanoparticles with a diameter in the range 17-22 nm on composite. Modification of carbon paste electrode (CPE) with Fe3O4@GO/OMC (Fe3O4@GO/OMC-CPE) allowed the ultrasensitive and selective detection of ALO at oxidation potential of 1.05 V with linear range of 0.05-7 µmol L-1, limit of detection of 47 nmol L-1 and sensitivity of 708 µA mmol-1 L. Also, the results demonstrate that charge transfer at the interface of Fe3O4@GO/OMC hybrid can provide a synergistic effect in comparison with Fe3O4@GO and OMC. The unique surface chemistry of Fe3O4@GO/OMC interface allows π-π stacking and electrostatic interactions with ALO. The advantages are the possibility to regenerate the surface of the sensor, its rapid and easy of production, as well as its applicability for detection of ALO in Tablets and human serum samples, making Fe3O4@GO/OMC-CPE promising interface for bio-electrochemical applications.


Assuntos
Alopurinol/sangue , Técnicas Biossensoriais/métodos , Carbono/química , Técnicas Eletroquímicas/métodos , Grafite/química , Nanopartículas de Magnetita/química , Comprimidos/análise , Antimetabólitos/sangue , Eletrodos , Humanos , Oxirredução
9.
Biosens Bioelectron ; 128: 159-165, 2019 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-30660931

RESUMO

Skin cancer is the most frequent kind of cancer in white people in many parts of the world. UV-induced DNA damage and genetic mutation can subsequently lead to skin cancer. Therefore development of new biosensing strategies for detection of UV-induced DNA damage is of great importance. Here we demonstrate a novel combination of an ex-vivo skin biointerface and an electrochemical DNA sensor for the direct detection of UV induced DNA damage and investigation the protective effect of various UV blockers (Zinc-oxide (ZnO), titanium-dioxide (TiO2) nanoparticles (NPs) and sunscreens) against DNA damage. A diazonium modified screen-printed carbon electrode immobilized with a DNA sequence related to the p53 tumour suppressor gene, the most commonly affected gene in human UV-induced skin cancer, was applied as an electrochemical DNA sensor. Electrochemical impedance spectroscopy (EIS) was employed for the detection of DNA damage induced by UV-A radiation by following the changes in charge transfer resistance (Rct). The protective effects of UV blockers applied onto a pig skin surface (a suitable model representing human skin) were successfully detected by the DNA sensor. We observed that the naked skin has little UV protection showing an 18.2% decreases in ∆R/R values compared to the control, while applying both NPs and NP-formulated sunscreens could significantly reduce DNA damage, resulting in a decrease in ∆R/R values of 67.1% (ZnO NPs), 77.2% (TiO2 NPs), 77.1% (sunscreen 1) and 92.4% (sunscreen 2), respectively. Moreover, doping moisturising cream with NPs could provide a similar DNA protective effect. This new method is a biologically relevant alternative to animal testing and offers advantages such as fast, easy and inexpensive processing, in addition to its miniaturised dimension, and could be used for a range of applications in other sources of DNA damage and the protective effect of different UV blocking agents and other topical formulations.


Assuntos
Técnicas Biossensoriais , Dano ao DNA/efeitos da radiação , DNA/isolamento & purificação , Proteína Supressora de Tumor p53/isolamento & purificação , Animais , DNA/química , Espectroscopia Dielétrica , Humanos , Nanopartículas Metálicas/química , Pele/patologia , Pele/efeitos da radiação , Protetores Solares/química , Suínos , Titânio/química , Proteína Supressora de Tumor p53/química , Proteína Supressora de Tumor p53/genética , Raios Ultravioleta , Óxido de Zinco/química
10.
Int J Biol Macromol ; 108: 1237-1241, 2018 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-29126942

RESUMO

A simple electrochemical DNA- based biosensor was designed for determination of Cd2+ using ethyl green (EG) as a DNA hybridization indicator on the surface of carbon paste electrode (CPE). The interaction of Cd2+ with double strand DNA (dsDNA) led to the destabilizing of dsDNA and the increase in the reduction peak currents of EG. The difference in the values of electrochemical responses of EG before and after DNA helix destabilization in the presence of Cd2+ (ΔI) was used for Cd2+ determination and was linearly related to the concentration of Cd2+ over the ranges of 1.0pM-1.0nM and 10.0nM-1.0µM. Detection limit was achieved as low as 0.3pM using simple and low cost working electrode and without applying any materials for modification of electrode or DNA. The proposed biosensor was utilized successfully to real sample analysis of Cd2+.


Assuntos
Técnicas Biossensoriais/métodos , Cádmio/análise , Cádmio/química , DNA/química , Sequência de Bases , Técnicas Biossensoriais/instrumentação , DNA/genética , Eletroquímica , Eletrodos , Desenho de Equipamento , Hibridização de Ácido Nucleico , Compostos de Amônio Quaternário/química
11.
Biosens Bioelectron ; 91: 650-657, 2017 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-28110249

RESUMO

The present work describes a label free electrochemical aptasensor for selective detection of epirubicin. In this project, 5'-thiole terminated aptamer was self-assembled on carbon screen printed electrode, which modified with electrodeposited gold nanoparticles on magnetic double-charged diazoniabicyclo [2.2.2] octane dichloride silica hybrid (Fe3O4@SiO2/DABCO) by Au-S bond. The interactions of epirubicin with aptamer on the AuNPs/Fe3O4@SiO2/DABCO/SPE have been studied by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy. Under optimized conditions, the peak current of epirubicin increased linearly with increasing epirubicin concentration, due to the switching in the aptamer conformation and formation of aptamer- epirubicin complex instead of aptamer on the modified electrode surface. The Apt/AuNPs/Fe3O4@SiO2/DABCO/SPE is sensitive, selective and has two linear range from 0.07µM to 1.0µM and 1.0µM to 21.0µM with a detection limit of 0.04µM. The applicability of the aptasensor was successfully assessed by determination of epirubicin in a human blood serum sample.


Assuntos
Antibióticos Antineoplásicos/sangue , Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais/métodos , Epirubicina/sangue , Ouro/química , Nanoestruturas/química , Técnicas Biossensoriais/instrumentação , Espectroscopia Dielétrica/instrumentação , Espectroscopia Dielétrica/métodos , Técnicas Eletroquímicas/instrumentação , Técnicas Eletroquímicas/métodos , Eletrodos , Galvanoplastia , Óxido Ferroso-Férrico/química , Humanos , Limite de Detecção , Nanoestruturas/ultraestrutura , Piperazinas/química , Dióxido de Silício/química
12.
Biosens Bioelectron ; 92: 630-637, 2017 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-27829554

RESUMO

Colorectal cancer is one of the most common cancers in the world and has no effective treatment. Therefore, development of new methods for early diagnosis is instantly required. Biological recognition probes such as synthetic receptor and aptamer is one of the candidate recognition layers to detect important biomolecules. In this work, an electrochemical aptasensor was developed by fabricating an aptamer-cell-aptamer sandwich architecture on an SBA-15-3-aminopropyltriethoxysilane (SBA-15-pr-NH2) and Au nanoparticles (AuNPs) modified graphite screen printed electrode (GSPE) surface for the selective, label-free detection of CT26 cancer cells. Based on the incubation of the thiolated aptamer with CT26 cells, the electron-transfer resistance of Fe (CN)63-/4- redox couple increased considerably on the aptasensor surface. The results obtained from cyclic voltammetry and electrochemical impedance spectroscopy studies showed that the fabricated aptasensor can specifically identify CT26 cells in the concentration ranges of 10-1.0×105cells/mL and 1.0×105-6.0×106 cells/mL, respectively, with a detection limit of 2cells/mL. Applying the thiol terminated aptamer (5TR1) as a recognition layer led to a sensor with high affinity for CT26 cancer cells, compared to control cancer cells of AGS cells, VERO Cells, PC3 cells and SKOV-3 cells. Therefore a simple, rapid, label free, inexpensive, excellent, sensitive and selective electrochemical aptasensor based on sandwich architecture was developed for detection of CT26 Cells.


Assuntos
Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais/métodos , Neoplasias Colorretais/diagnóstico , Espectroscopia Dielétrica/métodos , Animais , Linhagem Celular Tumoral , Chlorocebus aethiops , Colo/patologia , Técnicas Eletroquímicas/métodos , Eletrodos , Ouro/química , Grafite/química , Humanos , Nanopartículas Metálicas/química , Nanopartículas Metálicas/ultraestrutura , Camundongos , Reto/patologia , Sensibilidade e Especificidade , Células Vero
13.
Int J Biol Macromol ; 89: 421-7, 2016 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-27151665

RESUMO

Cytosine-rich DNA sequences can form a highly ordered structure known as i-motif in slightly acidic solutions. The stability of the folded i-motif structure is a good strategy to inhibit the telomerase reaction in cancer cells. The electrochemical biosensor was prepared by modifying carbon paste electrode with SiO2 nanoparticles to investigate drugs which can stabilize this structure. Tamoxifen (Tam), an antiestrogen hormonal agent for treatment of breast cancer, was chosen as the model ligand and its interaction with i-motif structure was examined. The interaction between i-motif DNA and Tam was studied in PBS buffer and [Fe(CN)6](3-) through the cyclic voltammetry and square wave voltammetry methods. The oxidation peak of Tam, due to the i-motif DNA/Tam interaction, was observed after i-motif immobilized on the surface of the electrode. The i-motif formation was investigated by circular dichroism spectroscopy and the results showed that this structure can certainly be made with pH around 4.5, but its stability reduced by going to the more alkaline pH. The selectivity which was studied in the presence of complementary strand demonstrated that i-motif structure could be stabilized in acidic pH even in the presence of its complementary strand.


Assuntos
Técnicas Biossensoriais , DNA/isolamento & purificação , Motivos de Nucleotídeos/genética , Tamoxifeno/isolamento & purificação , Citosina/química , DNA/química , Feminino , Humanos , Concentração de Íons de Hidrogênio , Nanopartículas/química , Dióxido de Silício/química , Tamoxifeno/química , Tamoxifeno/uso terapêutico
14.
Tumour Biol ; 37(7): 9967-77, 2016 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-26815508

RESUMO

The WT1 gene is an important oncogene, and its overexpression is considered as an effective target for anticancer therapy. Regulation of its gene transcription is one way for WT1-targeting drug design. Recently, in silico analysis of some oncogene promoters like WT1 showed some guanine-rich regions with the ability to form G-quadruplex structures. Ligands like 5,10,15,20-tetra(N-methyl-4-pyridyl)-porphine (TMPyP4) have predominant effect on G-quadruplex stabilization. The aim of this study was to understand the effect of TMPyP4 on WT1 gene transcription via stabilization of promoter G-quadruplexes. We examined the formation of new G-quadruplex motifs in WT1 promoter in the presence of TMPyP4. In order to understand the nature of its interaction with WT1 promoter quadruplexes, differential pulse voltammetry (DPV), circular dichroism (CD), polyacrylamide gel electrophoresis, electrophoretic mobility shift assay (EMSA), polymerase chain reaction (PCR) stop assays, and quantitative RT-PCR were performed. According to the results, the WT1 promoter can form stable intramolecular parallel G-quadruplexes. In addition, after 48 and 96 h of incubation, 100 µM TMPyP4 reduced the WT1 transcription to 9 and 0.4 %, respectively, compare to control. We report that ligand-mediated stabilization of G-quadruplexes within the WT1 promoter can silence WT1 expression. This study might offer the basis for the reasonable design and improvement of new porphyrin derivatives as effective anti-leukemia agents for cancer therapy.


Assuntos
DNA de Neoplasias/química , Quadruplex G , Regulação Neoplásica da Expressão Gênica , Leucemia Eritroblástica Aguda/genética , Porfirinas/metabolismo , Proteínas WT1/antagonistas & inibidores , Proliferação de Células , Dicroísmo Circular , Ensaio de Desvio de Mobilidade Eletroforética , Humanos , Leucemia Eritroblástica Aguda/metabolismo , Leucemia Eritroblástica Aguda/patologia , Ligantes , Modelos Moleculares , Porfirinas/genética , Regiões Promotoras Genéticas/genética , RNA Mensageiro/genética , Reação em Cadeia da Polimerase em Tempo Real , Reação em Cadeia da Polimerase Via Transcriptase Reversa , Células Tumorais Cultivadas , Proteínas WT1/genética , Proteínas WT1/metabolismo
15.
Int J Biol Macromol ; 83: 97-102, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26592696

RESUMO

The unique ability of living systems to translate biochemical reactions into mechanical work has inspired the design of synthetic DNA motors which generate nanoscale motion via controllable conformational change. It is believable that G-quadruplex structures in certain regions of the genome may play a role in the poor maintenance of genomic stability, which is a characteristic of many types of cancers. In this regards, formation and stabilization of the quadruplex structures at the telomeric repeats is an effective way to hamper the telomere extension and blocking the elongation step. Here, we report a DNA machine for selective Gquadruplex-binding ligand recognition, based on a conformational change; the forces exerted by the precise DNA machine for Gquadruplex conformational change were probed via an electrical signal transducer electrochemically by differential pulse voltammetry and cyclic voltammetry. The proposed machine was prepared by modifying the screen-printed graphite electrode (SPE) with the synthesized SBA-N-propylpipyrazine-N-(2-mercaptopropane-1-one) (SBA@NPPNSH) mesoporous structures and Au nanoparticles (AuNPs). The thiolated functionalized groups of SBA@NPPNSH structures can help for preconcentration of the synthesize AuNPs on the surface. Then SH-G4DNA was linked to the modified electrode by an AuNPsS bond. The morphology of constructed machine was characterized by the Field emission scanning electron microscope (FESEM).


Assuntos
Antineoplásicos/química , Antineoplásicos/farmacologia , Técnicas Biossensoriais/instrumentação , Quadruplex G/efeitos dos fármacos , Grafite/química , Nanopartículas/química , Técnicas Biossensoriais/métodos , DNA/química , DNA/genética , Eletrodos , Instabilidade Genômica/efeitos dos fármacos , Ligantes , Telômero/efeitos dos fármacos
16.
J Nanosci Nanotechnol ; 15(5): 3429-36, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-26504962

RESUMO

Simultaneous determination of N-acetyl-L-cysteine (NAC) and Tryptophan (Trp) has been studied at the surface of glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNTs) in the presence of 4-chlorocatechol as homogenous electrochemical catalyst in aqueous media. The electrocatalytic properties of GCE modified with MWCNTs in the presence of 4-chlorocatechol toward the electrocatalytic oxidation of NAC and Trp was studied using cyclic voltammetry (CV), double-step potential chronoamperometry and differential pulse voltammetry (DPV). The results has shown that NAC participates in Michael type addition reaction with electrogenerated quinone from electrooxidation of 4-chlorocatechol at MWCNT/GCE to form the corresponding thioquinone derivative. The reoxidation of the adduct leads to increase in the oxidative current which is proportional to the concentration of NAC. Differential pulse voltammogram peak currents of NAC and Trp increased linearly with their concentration at the ranges of 5-60 µM and 5-50 µM, respectively and the detection limits for NAC and Trp were sequentially 3.427 µM and 2.494 µM. The proposed method was successfully used for the determination of NAC in pharmaceutical samples and the obtained results were found to be reasonable.


Assuntos
Acetilcisteína/análise , Catecóis/química , Técnicas Eletroquímicas/métodos , Nanotubos de Carbono/química , Triptofano/química , Eletrodos , Limite de Detecção , Oxirredução
17.
Analyst ; 140(12): 4068-75, 2015 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-25884046

RESUMO

An electronic nanoswitch is described based on the conformational change of the DNA sequence in the presence of stabilizing ligands. The new electrochemical biosensor was prepared by modifying a screen-printed graphite electrode (SPE) with functionalized SiO2 nanoparticles [(SiO2-N-propylpiperazine-N-(2-mercaptopropane-1-one) (SiO2@NPPNSH)] and Au nanoparticles (AuNPs). These nanoparticles are able to immobilize thiolated G-quadruplex DNA structures (SH-G4DNA). The SH groups on the SiO2@NPPNSH nanoparticles provide a good platform for stabilizing AuNPs on the surface of the electrode. This is due to the fact that AuNPs are able to bind to the organic SH groups on the SiO2@NPPNSH. The SH-G4DNA binds to the modified electrode by a AuNPs-S bond. The structure of SiO2@NPPNSH was characterized by scanning electron microscopy (SEM), thermo-gravimetric analysis (TGA) and infrared (IR) spectroscopy. The morphology of the modified electrode was characterized by SEM. The interaction between G4DNA and the anticancer drug, Tamoxifen (Tam), was studied in Tris-HCl buffer and [Fe(CN)6](3-) using cyclic (CV) and square wave voltammetry (SWV). The G-quadruplex formation and the interaction mechanism were identified by circular dichroism (CD) measurements. The CV current was seen to decrease with increasing concentration of Tam due to interaction between G4DNA and Tam. This biosensor is a simple and useful tool for selecting G-quadruplex-binding ligands.


Assuntos
Antineoplásicos/análise , Técnicas Biossensoriais/métodos , Quadruplex G , Nanopartículas/química , Nanotecnologia/métodos , Telômero/química , Antineoplásicos/química , Sequência de Bases , Técnicas Biossensoriais/instrumentação , Eletroquímica , Eletrodos , Ferricianetos/química , Ouro/química , Grafite/química , Humanos , Nanotecnologia/instrumentação , Piperazina , Piperazinas/química , Dióxido de Silício/química , Tamoxifeno/análise , Tamoxifeno/química , Telômero/genética
18.
Mater Sci Eng C Mater Biol Appl ; 47: 77-84, 2015 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-25492175

RESUMO

In the present study, we report electrosynthesis of 4,5-bis(4-chloroanilino)-1,2-benzendiol (BCB) and its application as a selective electrochemical mediator at a surface of carbon paste electrode (CPE) modified ZnO/CNTs nanocomposite as a simple and rapid voltammetric sensor. The sensor showed an efficient catalytic activity for the electro-oxidation of glutathione (GSH), which leads to a lowered overpotential by more than 203 mV compared to unmodified carbon paste electrode. For the mixture containing GSH, nicotinamide adenine dinucleotide (NADH) and folic acid (FA), the electrooxidation signals were well separated. The square wave voltammetry (SWV) currents increased linearly with their concentration at the ranges of 0.006-161, 1.0-650 and 3.0-700 µM, respectively with the detection limits of 0.002, 0.3 and 1.0 µM. Finally, the electrode was successfully applied for the voltammetric determination of analytes in real samples with satisfactory results.


Assuntos
Técnicas Eletroquímicas/instrumentação , Ácido Fólico/análise , Glutationa/análise , NAD/análise , Nanotecnologia , Limite de Detecção , Microscopia Eletrônica de Transmissão , Oxirredução , Reprodutibilidade dos Testes
19.
Talanta ; 99: 277-82, 2012 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-22967552

RESUMO

It was firstly described, that a TiO(2) film modified titanium foil electrode (Ti/TiO(2)) shows an efficient photoelectrocatalytic activity towards formaldehyde oxidation in a phosphate buffer solution. Ti/TiO(2) foil electrode was prepared by anodizing Ti foil in aqueous solution. Also, this electrode was applied for the hydrodynamic photoamperometry measurement of formaldehyde in the optimum conditions (pH 7.0 as biological pH and bias potential 0.8 V vs. reference electrode). The photoelectrocatalytic oxidation photocurrent of the photoelectrode determined by photoamperometry method was linearly dependent on the formaldehyde concentration and the linearity range obtained was 6.70×10(-4)-1.48×10(-2) mol L(-1). Detection limit was found to be 3.09×10(-4) mol L(-1) (2σ).

20.
Bioelectrochemistry ; 85: 44-9, 2012 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-22243788

RESUMO

The electrocatalytic oxidation of amoxicillin was investigated on a nickel-based (Ni(II)-curcumin) chemically modified electrode. This modified electrode was prepared by electropolymerization of complex (curcumin = 1,7-bis[4-hydroxyl-3-methoxyphenyl]-1,6-heptadiene-3,5-dione) in alkaline solution. For the first time, the catalytic oxidation of amoxicillin was demonstrated by cyclic voltammetry, chronoamperometry, chronocoulometry and amperometry methods at the surface of this modified carbon paste electrode. The obtained results showed that NiOOH acts as an electrocatalyst for oxidation of amoxicillin. This electrocatalytic oxidation exhibited a good linear response for amoxicillin concentration over the range of 8 × 10⁻6-1×10⁻4 M with a detection limit of 5 × 10⁻6 M. Therefore, this electrocatalytic method was used as a simple, selective and rapid method able to determine amoxicillin in pharmaceutical preparations and biological media.


Assuntos
Amoxicilina/análise , Carbono/química , Curcumina/química , Técnicas Eletroquímicas/métodos , Níquel/química , Anti-Inflamatórios não Esteroides , Eletrodos , Limite de Detecção , Oxirredução
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