RESUMO
5, 7, 12, 14-pentacenetetrone (PT), polycyclic quinone derivatives, are rich in carbonyl, which were investigated as a novel organic electrode material for supercapacitors. PT with aπconjugated system, is a flat molecule, generating strongπ-πinteractions between molecules. PT molecules were uniformly fixed on conductive reduced graphene oxide (rGO) throughπ-πinteraction by one-step solvothermal method, forming a three-dimensional cross-linked PT@rGO hydrogel. This composite structure was conducive to reducing the charge transfer resistance and promoting the Faraday reaction of electrode, which achieved the superposition of electric double-layer capacitance and pseudocapacitance. Appropriate organic molecular loading can effectively improve electrochemical performance. The optimal PT@rGO electrode material displayed the specific capacitance of 433.2 F g-1at 5 mV s-1with an excellent rate capability in 1 mol l-1H2SO4electrolyte. Finally, the fully pseudocapacitive asymmetric supercapacitor has been assembled by using PT@rGO as positive electrode and benz[a]anthracene-7,12-quinone (BAQ) modified rGO(BAQ/rGO)as negative electrode, which exhibited the good energy storage performance in a cell voltage of 1.8 V.
RESUMO
Based on Ru(bpy)(3)(2+)-Au nanoparticles decorated multi-walled carbon nanotubes composites and a molecularly imprinted polymer (MIP), we propose a novel molecularly imprinted electrochemiluminescence (ECL) sensor to selectively determine isoniazid (INH). The MIP is synthesized through electrochemical copolymerization of acrylamide and N,N'-methylene diacrylamide in the presence of INH template molecules. The enhanced ECL intensity is linear in the range of 0.1 to 110 µg cm(-3) and the detection limit is 0.08 µg cm(-3) (3σ) INH with relative standard deviation 3.8% (n = 6) for 8 µg cm(-3). As a result, the sensor has been successfully applied to the determination of INH in human urine and pharmaceutical samples. Moreover, the possible ECL mechanism is discussed.
Assuntos
Técnicas de Química Analítica/instrumentação , Isoniazida/análise , Medições Luminescentes/métodos , Impressão Molecular/métodos , Acrilamidas/química , Eletroquímica , Eletrodos , Vidro/química , Ouro/química , Concentração de Íons de Hidrogênio , Isoniazida/química , Nanopartículas Metálicas/química , Nanotubos de Carbono/química , Compostos Organometálicos/químicaRESUMO
In this report, the theory based on thin-layer cyclic voltammetry (TLCV) for consecutive electron transfer (ET) across the interface between two immiscible electrolyte solutions (ITIES) is well developed and experimentally verified. The voltammetric responses to multistep electron transfer at the ITIES are predicted by numerical simulations. Moreover, the impact of empirical parameters on the shape of the multistep current-voltage curve has been examined. The results obtained not only give information regarding the effect of the concentration ratio of the reactants in two phases and the thin-layer thickness on multistep electron transfer, but also prove the excellent agreement between simulations and experiments. The model system of two-step electron transfer of ZnTPP/[Fe(CN)6]4â» was studied, indicating that the Bulter-Volmer (B-V) theory is suitable for the consecutive electron transfer. Thus, TLCV is demonstrated to be a useful means for investigating the kinetics of heterogeneous consecutive ET.
RESUMO
2,3,4-Trihydroxyacetophenone was synthesized with pyrogallol. Benzoylhydrazone and p-hydroxybenzoylhydrazone were synthesized using the reaction of ethyl benzoate and methyl p-hydroxybenzoate with hydrazine hydrate. Three novel 2,3,4-trihydroxyacetophenone hydrazones were synthesized using the reaction of 2,3,4-trihydroxyacetophenone with benzoylhydrazone, p-hydroxybenzoylhydrazone and phenylhydrazine. IR, UV and the fluorescence spectrum of 2,3,4-trihydroxyacetophenone hydrazones were studied.
Assuntos
Acetofenonas/química , Hidrazonas/química , Hidrazonas/síntese química , Análise Espectral , Modelos Químicos , Estrutura Molecular , Fenil-Hidrazinas/química , Pirogalol/química , Espectrometria de Fluorescência , Espectrofotometria Infravermelho , Espectrofotometria UltravioletaRESUMO
A novel molecularly imprinted (MIP) impedimetric sensor was promoted for selective detecting melamine (MEL). The Au electrode modified with MIP poly (2-mercaptobenzimidazole) (PMBI) was prepared by electrochemical polymerization of 2-mercaptobenzimidazole (2-MBI) with cyclic voltammetry (CV) in the presence of template molecule MEL. The surface morphology and structure of MIP PMBI are characterized by atomic force microscopy (AFM), infrared spectra (IR), electrochemical impedance spectroscopy (EIS), and CV. The main driving force of recognition is the π-donor-acceptor interaction between MEL and PMBI. The imprinted electrode could avoid the interference successfully. In addition, a linear response curve was obtained from 1.0×10(-8) M to 5.0×10(-5) M, with the detection limit of 3.0×10(-9) M. The sensor exhibits remarkable advantages, such as higher sensitivity, wider linear range and lower detection limit. The effective method has a potential application to monitor nonelectrochemically active substances in food analysis in the future.
Assuntos
Espectroscopia Dielétrica/instrumentação , Impressão Molecular , Triazinas/análise , Limite de Detecção , Microscopia de Força Atômica , Espectrofotometria InfravermelhoRESUMO
The hydroxide of meso-tetraphenylporphyrin derivatives functionalized carbon nanotubes (CNTs) was fabricated in our research to explore the interaction between porphyrin and explosive. It was turned out that in the formation of grid porphyrin film, carbon nanotubes as a cruciul base materials promoted the electron transfer rate. Most of important, the results also showed that the electrochemical response was enhanced through increasing the number of -OH substitution in porphyrin. Such information provides the platform for a practical strategy for rational design of the sensor of explosives.
Assuntos
Eletrodos , Substâncias Explosivas/química , Nanotubos de Carbono/química , Porfirinas/químicaRESUMO
A novel electrochemical sensor based on molecularly imprinted polymer film has been developed for aspirin detection. The sensitive film was prepared by co-polymerization of p-aminothiophenol (p-ATP) and HAuCl(4) on the Au electrode surface. First, p-ATP was self-assembled on the Au electrode surface by the formation of Au-S bonds. Then, the acetylsalicylic acid (ASA) template was assembled onto the monolayer of p-ATP through the hydrogen-bonding interaction between amino group (p-ATP) and oxygen (ASA). Finally, a conductive hybrid membrane was fabricated at the surface of Au electrode by the co-polymerization in the mixing solution containing additional p-ATP, HAuCl(4) and ASA template. Meanwhile, the ASA was spontaneously imprinted into the poly-aminothiophenol gold nanoparticles (PATP-AuNPs) complex film. The amount of imprinted sites at the PATP-AuNPs film significantly increases due to the additional replenishment of ASA templates. With the significant increasing of imprinted sites and doped gold nanoparticles, the sensitivity of the molecular imprinted polymer (MIP) electrode gradually increased. The molecularly imprinted sensor was characterized by electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV), and cyclic voltammetry (CV). The linear relationships between current and logarithmic concentration were obtained in the range from 1 nmol L(-1) to 0.1 µmol L(-1) and 0.7 µmol L(-1) to 0.1 mmol L(-1). The detection limit of 0.3 nmol L(-1) was achieved. This molecularly imprinted sensor for the determination of ASA has high sensitivity, good selectivity and reproducibility, with the testing in some biological fluids also has good selectivity and recovery.
Assuntos
Aspirina/sangue , Aspirina/urina , Técnicas Biossensoriais/métodos , Técnicas Eletroquímicas/métodos , Polímeros/química , Compostos de Anilina/química , Aspirina/química , Técnicas Biossensoriais/instrumentação , Cloretos/química , Técnicas Eletroquímicas/instrumentação , Eletrodos , Ouro/química , Compostos de Ouro/química , Humanos , Microscopia Eletrônica de Varredura , Impressão Molecular , Estrutura Molecular , Reprodutibilidade dos Testes , Saliva/química , Compostos de Sulfidrila/químicaRESUMO
Porphyrin is able to specifically combine with phosphorus, thus a novel bifunctional sensing platform for determination of porphyrin by visual colorimetry and electrochemistry was demonstrated. A pretreated gold sheet (or electrode) with 2-mercatpoethanol (2-ME) was chemically modified by POCl(3) to obtain the surface phosphate active sites. The different stages of modified electrode were characterized by electrochemical impedance spectroscopy (EIS). The 1:1 cationic sitting-atop (SAT) complex P(V)-porphyrin was formed due to the high affinity of the modified gold sheet (or electrode) towards the porphyrin, resulting in electron transfer resistance increase of the electrode surface. Meanwhile, a dramatic color changing from burgundy to dark green of porphyrin solution was observed with the naked-eye within 3s. What's more, this was reflected by the notable change of the Soret band of porphyrin when using UV-vis. Two sensing systems provide different sensitivity for porphyrin analysis. With visual colorimetry, porphyrin can be detected at a level of 1.0×10(-6) M, whereas the detection limit of porphyrin is 3.0×10(-8) M using the EIS method. The practical application of the sensor to determination of pheophytin which was obtained from fresh spinach leaves has been accomplished. The results demonstrate the facility and effectivity of our introduced bifunctional biosensor for quantitative analysis of porphyrin.