RESUMO
On-site hydrogen peroxide production through electrocatalytic and photocatalytic oxygen reduction reactions has recently attracted broad research interest. However, practical applications have thus far been plagued by the low activity and the requirement of complex equipment. Here, inspired by the process of biological hydrogen peroxide synthesis catalyzed by enzymes, we report a Pt-Au alloy to mimic the catalytic function of natural formate oxidase for hydrogen peroxide synthesis through aerobic oxidation of formic acid. The mass activity of the Pt-Au alloy is three times higher than that of formate oxidase. Density functional theory calculations revealed that the efficient dehydrogenation of formic acid and the high selectivity of the subsequent reduction of oxygen to hydrogen peroxide account for the high hydrogen peroxide productivity. In addition, the formic acid aqueous solution provides an acidic environment, which is conducive to the utilization of the in situ generated hydrogen peroxide for oxidation reactions, including C-H bond oxidation and sterilization.
Assuntos
Peróxido de Hidrogênio , Platina , Platina/química , Ligas de Ouro , Formiatos/química , Oxirredução , Ligas/química , Oxirredutases , OxigênioRESUMO
In this work, the effective fluorescence quenching ability of polydopamine nanotubes (PDANTs) toward various fluorescent dyes was studied and further applied to fluorescent biosensing for the first time. The PDANTs could quench the fluorophores with different emission frequencies, aminomethylcoumarin acetate (AMCA), 6-carboxyfluorescein (FAM), 6-carboxytetramethylrhodamine (TAMRA), and Cy5. All the quenching efficiencies reached to more than 97%. Taking advantage of PDANTs' different affinities toward ssDNA and dsDNA and utilizing the complex of FAM-labeled ssDNA and PDANTs as a sensing platform, we achieved highly sensitive and selective detection of human immunodeficiency virus (HIV) DNA and adenosine triphosphate (ATP) assisted with Exonuclease III amplification. The limits of detection (LODs) of HIV DNA and ATP reached to 3.5 pM and 150 nM, respectively, which were all lower than that of previous nanoquenchers with Exo III amplification, and the platform also presented good applicability in biological samples. Fluorescent sensing applications of this nanotube enlightened other targets detection based upon it and enriched the building blocks of fluorescent sensing platforms. This polydopamine nanotube also possesses excellent biocompatibility and biodegradability, which is suitable for future drug delivery, cell imaging, and other biological applications.
Assuntos
Trifosfato de Adenosina/análise , Técnicas Biossensoriais/métodos , DNA Viral/análise , Corantes Fluorescentes/química , HIV/isolamento & purificação , Indóis/química , Nanotubos/química , Polímeros/química , Trifosfato de Adenosina/sangue , Animais , Bovinos , Exodesoxirribonucleases/metabolismo , Infecções por HIV/virologia , Humanos , Limite de Detecção , Nanotubos/ultraestrutura , Espectrometria de Fluorescência/métodosRESUMO
We have demonstrated a rapid and general strategy to synthesize novel three-dimensional PdPt bimetallic alloy nanosponges in the absence of a capping agent. Significantly, the as-prepared PdPt bimetallic alloy nanosponges exhibited greatly enhanced activity and stability towards ethanol/methanol electrooxidation in an alkaline medium, which demonstrates the potential of applying these PdPt bimetallic alloy nanosponges as effective electrocatalysts for direct alcohol fuel cells. In addition, this simple method has also been applied for the synthesis of AuPt, AuPd bimetallic, and AuPtPd trimetallic alloy nanosponges. The as-synthesized three-dimensional bimetallic/trimetallic alloy nanosponges, because of their convenient preparation, well-defined sponge-like network, large-scale production, and high electrocatalytic performance for ethanol/methanol electrooxidation, may find promising potential applications in various fields, such as formic acid oxidation or oxygen reduction reactions, electrochemical sensors, and hydrogen-gas sensors.
Assuntos
Ligas/química , Boroidretos/química , Técnicas Eletroquímicas , Etanol/química , Nanopartículas Metálicas/química , Metanol/química , Catálise , Oxirredução , Paládio/química , Platina/químicaRESUMO
Taking advantage of strand-displacement DNA polymerization and parallel-motif DNA triplex system as dual amplifications, a new electrochemical label-free integrated aptasensor based on silver microspheres (SMSs) as a separation element and graphene-mesoporous silica-gold nanoparticle (NP) hybrids (GSGHs) as an enhanced element of the sensing platform was first reported. In this sensing design (schematic representation of the sensing procedure for adenosine triphosphate detection, Scheme 1 in manuscript text), which contains an enhanced three-step magnification process, SMSs with "clean" surface were first used to separate the undesirable aptamer and aptamer-adenosine triphosphate (ATP) complex attached on SMSs surface after aptamer-ATP interaction, which lead to the detachment of blocker DNA into the solution phase. Then, under the assistance of blocker DNA, an amplified method based on the inherent signal-transduction mechanism of the hairpin probe and strand-displacement property of DNA polymerase was introduced. The obtained duplex DNA was used to hybridize with an acceptor DNA assembled on electrode to form triplex DNA, which could bring a more obvious detection signal compared with the duplex DNA without the amplification. The electrochemical signal came from the GSGH-based enhanced sensing interface containing positively charged ferrocene-appended poly(ethyleneimine) (Fc-PEI). Using the above multiple effects, we could achieve the sensitive analysis of a model small molecule-ATP (an important "molecular currency" of intracellular energy transfer) in a wide detection range from 0.05 nM to 56.5 nM with the detection limit of 0.023 nM.
Assuntos
Aptâmeros de Nucleotídeos/química , Técnicas Eletroquímicas , Ouro/química , Grafite/química , Nanopartículas Metálicas/química , Dióxido de Silício/química , Prata/química , Trifosfato de Adenosina/análise , Trifosfato de Adenosina/sangue , Técnicas Biossensoriais , Compostos Ferrosos/química , Humanos , Cinética , Metalocenos , Polietilenoimina/químicaRESUMO
Aptamers, which are artificial oligonucleotides selected in vitro, have been employed to design novel biosensors (i.e., aptasensors). In this work, we first constructed a label-free electrochemical aptasensor introducing a probe immobilization technique by the use of a layer-by-layer (LBL) self-assembled multilayer with ferrocene-appended poly(ethyleneimine) (Fc-PEI) on an indium tin oxide (ITO) array electrode for detection of cocaine. The Fc-PEI and gold nanoparticles (AuNPs) were LBL assembled on the electrode surface via electrostatic interaction. Then, cocaine aptamer fragments, SH-C2, were covalently labeled onto the outermost AuNP layer. When the target cocaine and cocaine aptamer C1 were present simultaneously, the SH-C2 layer hybridized partly with C1 to bind the cocaine, which led to a decreased differential pulse voltammetry (DPV) signal of Fc-PEI. This DPV signal change could be used to sensitively detect cocaine with the lowest detectable concentration down to 0.1 microM and the detection range up to 38.8 microM, which falls in the the expected range for medical use of detecting drug abuse involving cocaine. Meanwhile, the sensor was specific to cocaine in complex biologic fluids such as human plasma, human saliva, etc. The sensing strategy had general applicability, and the detection of thrombin could also be realized, displayed a low detection limit, and exhibited worthiness to other analytes. The aptasensor based on the array electrode held promising potential for integration of the sensing ability in multianalysis for simultaneous detection.
Assuntos
Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais/métodos , Cocaína/análise , Animais , Aptâmeros de Nucleotídeos/genética , Sequência de Bases , Bovinos , Cocaína/sangue , Cocaína/química , Cocaína/urina , Eletrodos , Compostos Ferrosos/química , Ouro/química , Humanos , Nanopartículas Metálicas/química , Metalocenos , Hibridização de Ácido Nucleico , Polietilenoimina/química , Reprodutibilidade dos Testes , Trombina/análiseRESUMO
We have demonstrated the design of a new type fluorescent assay based on the inner filter effect (IFE) of metal nanoparticles (NPs), which is conceptually different from the previously reported metal NPs-based fluorescent assays. With a high extinction coefficient and tunable plasmon absorption feature, metal NPs are expected to be capable of functioning as a powerful absorber to tune the emission of the fluorophore in the IFE-based fluorescent assays. In this work, we presented two proof-of-concept examples based on the IFE of Au NPs by choosing MDMO-PPV as a model fluorophore, whose fluorescence could be tuned by the absorbance of Au NPs with a much higher sensitivity than the corresponding absorbance approach. While the first assay worked in a turn-on mode upon the etching of Au NPs by the analyte, CN(-), the second one functioned in a turn-off mode upon the catalytic growth of Au NPs by the analyte, H(2)O(2). As a result, the present IFE-based approach can detect cyanide ranging from 1.0 x 10(-6) to 6.0 x 10(-4) M with a detection limit of 6.0 x 10(-7) M and H(2)O(2) ranging from 1.5 x 10(-7) to 2.2 x 10(-5) M with a detection limit of 8.5 x 10(-8) M, respectively. Notably, the present IFE-based approach allows the design of fluorescent assays in a more simple, time-saving, and economical approach when compared with conventional metal NPs-based fluorescent assays, since no modification step of the fluorophore was needed any more.
Assuntos
Cianetos/análise , Filtração , Fluorescência , Peróxido de Hidrogênio/análise , Nanopartículas Metálicas/química , Catálise , Ouro/química , Polivinil/química , Espectrometria de FluorescênciaRESUMO
Here, a fluorescent switch is constructed combining hemin, hemin aptamer, and a newly synthesized anionic conjugated polymer (ACP), poly(9,9-bis(6'-phosphatehexyl) fluorenealt-1,4-phenylene) sodium salt (PFHPNa/PFP). In the "off-state", the fluorescence of PFP is sensitively quenched by hemin, with a high K(sv) value of approximately 10(7). While in the "on-state", the formation of the aptamer/hemin complex recovers the fluorescence intensity. The fluorescent switch is sensitive and selective to hemin. To testify the universality and practicality of the fluorescent switch, a series of label-free DNA-related sensing platforms are developed, containing three DNA sensing strategies and one ATP recognition strategy. The fluorescent switch developed is simple, sensitive, and universal, which extends applications of the anionic conjugated polymers.
Assuntos
Técnicas Biossensoriais/métodos , DNA/análise , Corantes Fluorescentes/química , Hemina/análise , Polímeros/química , Trifosfato de Adenosina/análise , Aptâmeros de Peptídeos/química , Sequência de Bases , DNA/genética , Corantes Fluorescentes/metabolismo , Espectrometria de Fluorescência , Coloração e RotulagemRESUMO
In this work, rapid fabrication of Au nanoparticle (Au NP) films has been simply achieved by alternate adsorption of citrate-stabilized Au NPs and poly(diallyldimethylammonium chloride) with the aid of centrifugal force. In contrast to conventional electrostatic assembly, we carried out the assembly process in a centrifuge with a rotating speed of 4000 rpm, where centrifugal force can be imposed on Au NPs. Scanning electron microscopy and cyclic voltammetry were employed to characterize the assembly procedure and the thus-prepared thin solid films. Our results demonstrate that centrifugal force can promote the assembly of Au NPs and therefore enable the rapid fabrication of functional Au NP films. The thus-prepared Au NP films can serve as surface enhanced Raman scatting (SERS) substrates with tunable SERS signal intensity. This method is simple, rapid, and can be used as a general method to rapidly assemble other charged nanoparticles.
Assuntos
Centrifugação/métodos , Cristalização/métodos , Ouro/química , Membranas Artificiais , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Nanotecnologia/métodos , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
The formaldehyde biosensors with the features of cost effectiveness, high specificity, easy operation, and simplicity are urgently desired in routing and field detection of formaldehyde. Here, we report a new design of an enzymatic self-powered biosensor (ESPB) toward formaldehyde detection. The ESPB involves a formaldehyde dehydrogenase/poly-methylene green/buckypaper bioanode as the sensing electrode and a Prussian blue/Au nanoparticles/carbon fiber paper cathode as the electrochromic display. Formaldehyde acts as the fuel to drive the ESPB, relying on that the concentration of formaldehyde can be determined with the ESPB by both directly measuring the variance in short circuit current and observing the color change of the cathode. By measuring the variance in short circuit current, a linear detection range from 0.01 to 0.35 mM and a calculated detection limit of 0.006 mM are obtained, comparable to or better than those reported before. The color change of the cathode can be distinguished easily and exactly via the naked eye after immersing the ESPB in formaldehyde solution for 90 s with the concentration up to 0.35 mM, covering the permissive level of formaldehyde in some standards associated with environmental quality control. Specially, the formaldehyde concentration can be precisely quantified by analyzing the color change of the cathode digitally using the equation of B/(R + G + B). In the following test of real spiked samples of tap water and lake water, the recovery ratios of formaldehyde with the concentrations from 0.010 to 0.045 mM are tested to be between 95 and 100% by both measuring the variance in short circuit current and analyzing the color change of the cathode digitally. In addition, the ESPB exhibits negligible interference from acetaldehyde and ethanol and can be stored at 4 °C for 21 days with a loss of less than 8% in its initial value of short circuit current. Therefore, the ESPB with the capability of working like disposable test paper can be expected as a sensitive, simple, rapid, cost-effective colorimetric method with high selectivity in routing and field formaldehyde detection.
Assuntos
Técnicas Biossensoriais , Formaldeído/análise , Aldeído Oxirredutases/química , Colorimetria , Técnicas Eletroquímicas , Eletrodos , Formaldeído/química , Ouro/química , Chumbo/química , Nanopartículas Metálicas/química , Azul de Metileno/análogos & derivados , Azul de Metileno/química , Polietilenotereftalatos/química , Compostos de Estanho/químicaRESUMO
Nanozymes provide comparative advantages over natural enzymes and conventional artificial enzymes for catalytic reactions. However, nanozymes are only suitable for limited types of reactions, whose catalytic principles are not yet fully revealed. Herein, a new nanozyme based on a bionic zeolitic imidazolate framework is proposed. Zeolitic imidazolate framework-8 (ZIF-8) possesses a similar geometric structure to that of the active center of human carbonic anhydrase II (hCAII) and exhibits catalytic performance analogous to that of the hCAII. The less imidazolate coordinated zinc cations on the external surface of ZIF-8 can act as Lewis acid sites, lowering the pKa of Zn-bound H2O molecules from 14 to 8.4, which facilitates the deprotonation of H2O molecules and generation of zinc-bound hydroxide nucleophiles. The esterase-like ZIF-8 nanozyme shows a similar affinity to p-nitrophenyl acetate compared with hCAII. The ZIF-8 nanozyme also promotes CO2 hydration and acetylthiocholine hydrolysis reaction, and a series of ZIFs are also found with intrinsic enzyme-like activities due to similar compositions and spatial structures. These results imply that the bionic nanoparticles can be developed to fabricate a new generation of nanozymes by mimicking the active sites of natural enzymes.
Assuntos
Materiais Biocompatíveis/química , Imidazóis/química , Estruturas Metalorgânicas/química , Zeolitas/química , Acetiltiocolina/química , Acetiltiocolina/metabolismo , Materiais Biocompatíveis/metabolismo , Dióxido de Carbono/química , Anidrase Carbônica II/química , Catálise , Domínio Catalítico , Humanos , Hidrólise , Estruturas Metalorgânicas/metabolismo , Nitrofenóis/química , Nitrofenóis/metabolismoRESUMO
Here, we report a sensitive amplified electrochemical impedimetric aptasensor for thrombin, a kind of serine protease that plays important role in thrombosis and haemostasis. For improving detection sensitivity, a sandwich sensing platform is fabricated, in which the thiolated aptamers are firstly immobilized on a gold substrate to capture the thrombin molecules, and then the aptamer functionalized Au nanoparticles (AuNPs) are used to amplify the impedimetric signals. Such designed aptamer/thrombin/AuNPs sensing system could not only improve the detection sensitivity compared to the reported impedimetric aptasensors but also provide a promising signal amplified model for aptamer-based protein detection. In this paper, we realize a sensitive detection limit of 0.02 nM, with a linear range of 0.05-18 nM. Meanwhile, the effect of 6-mercaptohexanol (MCH) and 2-mercaptoethanol (MCE) on the modification of the electrode is investigated.
Assuntos
Amplificadores Eletrônicos , Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais/instrumentação , Eletroquímica/instrumentação , Ouro/química , Nanopartículas/química , Trombina/análise , Técnicas Biossensoriais/métodos , Materiais Revestidos Biocompatíveis/química , Eletroquímica/métodos , Desenho de Equipamento , Análise de Falha de Equipamento , Nanopartículas/ultraestrutura , Tamanho da Partícula , Reprodutibilidade dos Testes , Sensibilidade e EspecificidadeRESUMO
A layer-by-layer film composed of DNA and inorganic zirconium ion (Zr(4+)) was fabricated on the surface of gold thin film, and an electric field triggered disintegration of the multilayer film was studied by using electrochemical surface plasmon resonance (EC-SPR). EC-SPR results demonstrated that the film was disassembled upon the application of an electric field and the disassembly rate varied with the applied potential, leading to the controlled release of DNA. The electrodissolution could be switched off by removing the electric potential and reactivated by reapplying the potential. By incorporating plasmid DNA (pDNA) in to this controlled release system, the multilayer film could sustain the consecutive release of pDNA electrochemically. The released pDNA retained its integrity and transfection activity, and expressed enhanced green fluorescent protein (EGFP) after being transfected into HEK 293 cells. The electrochemical systems, with advantages of miniaturization, surface-tailoring, safety, simplicity, convenience, automation, low-cost, and free of immune reactions, made the electrical route a very attractive gene-delivery alternative.
Assuntos
Materiais Biocompatíveis/química , DNA/química , Eletroquímica/métodos , Íons , Técnicas de Transferência de Genes , Vetores Genéticos/química , Proteínas de Fluorescência Verde/química , Humanos , Concentração de Íons de Hidrogênio , Compostos Inorgânicos/química , Plasmídeos/metabolismo , Ressonância de Plasmônio de Superfície , Propriedades de Superfície , Transfecção , Zircônio/químicaRESUMO
We report a new approach for the synthesis of fluorescent and water-soluble Ag nanoclusters, using the common polyelectrolyte poly(methacrylic acid) as the template.
Assuntos
Nanopartículas Metálicas/química , Ácidos Polimetacrílicos/química , Prata/química , Eletrólitos/química , Fluorescência , Solubilidade , Espectrometria de Fluorescência/métodos , Água/químicaRESUMO
A simple, rapid and ultrasensitive colorimetric detection of protein using aptamer-Au nanoparticles (AuNPs) conjugates based on a dot-blot array has been developed, which was combined with the unique optical properties of AuNPs, enabling the visual detection of protein within minutes without any instrument.
Assuntos
Aptâmeros de Nucleotídeos/química , Ouro/química , Nanopartículas Metálicas/química , Proteínas/análise , Colódio/química , Colorimetria/métodos , Humanos , Membranas Artificiais , Reprodutibilidade dos Testes , Prata/química , Trombina/análiseRESUMO
Molecular logic devices with various functions play an indispensable role in molecular data transmission/processing. However, during any kinds of data transmission, a constant and unavoidable circumstance is the appearance of bit errors, which have serious effects on the regular logic computation. Fortunately, these errors can be detected via plugging a parity generator (pG) at the transmitting terminal and a parity checker (pC) at the receiving terminal. Herein, taking advantage of the efficient adsorption/quenching ability of polydopamine nanospheres toward fluorophore-labeled single-stranded DNA, we explored this biocompatible nanomaterial to DNA logic computation and constructed the first simple, enzyme-free, and G-quadruplex-free DNA pG/pC for error detection through data transmission. Besides, graphene oxide (GO) was innovatively introduced as the "corrective element" to perform the output-correction function of pC. All the erroneous outputs were corrected to normal conditions completely, ensuring the regular operation of later logic computing. The total operation of this non-G4 pG/pC system (error checking/output-correction) could be completed within 1 h (about 1/3 of previous G4 platform) in a simpler and more efficient way. Notably, the odd pG/pC with analogous functions was also achieved through negative logic conversion to the fabricated even one. Furthermore, the same system could also perform three-input concatenated logic computation (XOR-INHIBIT), enriching the complexity of PDs-based logic computation.
Assuntos
Nanosferas , DNA , Quadruplex G , Indóis , PolímerosRESUMO
The monitoring of toxicity of water is very important to estimate the safety of drinking water and the level of water pollution. Herein, a small microbial three-electrode cell (M3C) biosensor filled with polystyrene particles was proposed for online monitoring of the acute water toxicity. The peak current of the biosensor related with the performance of the bioanode was regarded as the toxicity indicator, and thus the acute water toxicity could be determined in terms of inhibition ratio by comparing the peak current obtained with water sample to that obtained with nontoxic standard water. The incorporation of polystyrene particles in the electrochemical cell not only reduced the volume of the samples used, but also improved the sensitivity of the biosensor. Experimental conditions including washing time with PBS and the concentration of sodium acetate solution were optimized. The stability of the M3C biosensor under optimal conditions was also investigated. The M3C biosensor was further examined by formaldehyde at the concentration of 0.01%, 0.03%, and 0.05% (v/v), and the corresponding inhibition ratios were 14.6%, 21.6%, and 36.4%, respectively. This work provides a new insight into the development of an online toxicity detector based on M3C biosensor.
Assuntos
Fontes de Energia Bioelétrica , Técnicas Biossensoriais/instrumentação , Água Potável/química , Poluentes Químicos da Água/análise , Eletroquímica , Eletrodos , Concentração de Íons de Hidrogênio , Poliestirenos/química , Segurança , Acetato de Sódio/química , Temperatura , Poluentes Químicos da Água/toxicidadeRESUMO
Fully sulfonated polyaniline nano-particles, nano-fibrils and nano-networks have been achieved for the first time by electrochemical homopolymerization of orthanilic acid using a three-step electrochemical deposition procedure in a mixed solvent of acetonitrile (ACN) and water. The diameter of the uniform nano-particles is about 60 nm, and the nano-fibrils can be organized in two-dimensional (2D) or three-dimensional (3D) non-periodic networks with good electrical contact. Average distance between contacts is about 850 and 600nm for a 2D and 3D system, respectively. The details of the poly(orthanilic acid) (POA) nano-structure were examined with a field emission scanning electron microscope (SEM). The structure and properties of POA were characterized with FTIR, UV-vis and electrochemical methods. The 3D POA nano-networks coated platinum electrode gave a direct electrochemical behavior of horse heart cytochrome c (Cyt c) immobilized on this electrode surface, a pair of well-defined redox waves with formal potential (E( degrees ')) of -0.032 V (versus Ag/AgCl) was achieved. The interaction between Cyt c and POA makes the formal potential shift negatively compared to that of Cyt c in solution. Spectrophotometric and electrochemical methods were used to investigate the interaction of Cyt c with POA. The immobilized Cyt c in the nano-networks POA film maintained its activity, showing a surface-controlled electrode process with the electron transfer rate constant (k(s)) of 21s(-1) and a of 0.53, and could be used for the electrocatalytic reduction of hydrogen peroxide. The quantitative determination of Cyt c by differential pulse voltammetry (DPV) using the fully sulfonated 3D POA nano-networks film coated platinum electrode was also studied.
Assuntos
Compostos de Anilina/química , Técnicas Biossensoriais/instrumentação , Citocromos c/análise , Citocromos c/química , Eletroquímica/instrumentação , Peróxido de Hidrogênio/análise , Nanoestruturas/química , Técnicas Biossensoriais/métodos , Materiais Revestidos Biocompatíveis/química , Eletroquímica/métodos , Desenho de Equipamento , Análise de Falha de Equipamento , Compostos de Enxofre/químicaRESUMO
Gold nanoparticles have been attached onto glassy carbon electrode surface through sulfhydryl-terminated monolayer and characterized by X-ray photoelectron spectroscopy, atomic force microscopy, electrochemical impedance spectroscopy and cyclic voltammetry. The gold nanoparticles-attached glassy carbon electrodes have been applied to the immobilization/adsorption of hemoglobin, with a monolayer surface coverage of about 2.1 x 10(-10) mol cm(-2), and consequently obtained the direct electrochemistry of hemoglobin. Gold nanoparticles, acting as a bridge of electron transfer, can greatly promote the direct electron transfer between hemoglobin and the modified glassy carbon electrode without the aid of any electron mediator. In phosphate buffer solution with pH 6.8, hemoglobin shows a pair of well-defined redox waves with formal potential (E0') of about -0.085 V (versus Ag/AgCl/saturated KCl). The immobilized hemoglobin maintained its biological activity, showing a surface controlled electrode process with the apparent heterogeneous electron transfer rate constant (ks) of 1.05 s(-1) and charge-transfer coefficient (a) of 0.46, and displays the features of a peroxidase in the electrocatalytic reduction of hydrogen peroxide. A potential application of the hemoglobin-immobilized gold nanoparticles modified glassy carbon electrode as a biosensor to monitor hydrogen peroxide has been investigated. The steady-state current response increases linearly with hydrogen peroxide concentration from 2.0 x 10(-6) to 2.4 x 10(-4) M. The detection limit (3sigma) for hydrogen peroxide is 9.1 x 10(-7) M.
Assuntos
Técnicas Biossensoriais/instrumentação , Eletroquímica/instrumentação , Ouro/química , Hemoglobinas/análise , Hemoglobinas/química , Peróxido de Hidrogênio/análise , Peróxido de Hidrogênio/química , Técnicas Biossensoriais/métodos , Carbono/química , Catálise , Materiais Revestidos Biocompatíveis/análise , Materiais Revestidos Biocompatíveis/química , Eletroquímica/métodos , Desenho de Equipamento , Análise de Falha de Equipamento , Vidro/química , Microeletrodos , Nanotubos/análise , Nanotubos/química , Nanotubos/ultraestrutura , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Electrochemically synthesized conducting polymer polypyrrole (PPy) film on gold electrode surface was used as a novel support for bilayer lipid membranes (BLMs). Investigations by surface plasmon resonance (SPR) suggest that dimyristoyl-L-alpha-phosphatidylcholine (DMPC) and dimyristoyl-L-alpha-phosphatidyl-L-serine (DMPS) can form BLMs on PPy film surface but dimyristoyl-L-alpha-phosphatidylglycerol (DMPG) and didodecyldimethylammonium bromide (DDAB) can not do so, indicating the formation of PPy supported bilayer lipid membranes (s-BLMs) is dependent on the chemical structure of the lipids used. The self-assembly of DMPC induces a smoother topography than the PPy layer with rms roughness decreasing from 4.484 to 2.914 nm convinced by atomic force microscopy (AFM). Impedance spectroscopy measurements confirm that the deposition of BLM substantially increases the resistance of the system indicating a very densely packed BLM structures. The little change of PPy film in capacitance shows that solvent and electrolyte ions still retain within the porous PPy film after BLM deposition. Therefore, the PPy supported BLM is to some extent comparable to conventional BLM with aqueous medium retaining at its two sides. As an example and preliminary application, horseradish peroxidase (HRP) reconstituted into the s-BLM shows the expected protein activity and can transfer electron from or to the underlying PPy support for its response to electrocatalytic reduction of hydrogen peroxide in solution. Thus the system maybe possesses potential applications to biomimetic membrane studies.
Assuntos
Técnicas Biossensoriais/instrumentação , Bicamadas Lipídicas , Polímeros , Pirróis , Eletrodos , Microscopia de Força AtômicaRESUMO
A new type of sol-gel-derived titanium oxide/copolymer composite material was developed and used for the construction of glucose biosensor. The composite material merged the best properties of the inorganic species, titanium oxide and the organic copolymer, poly(vinyl alcohol) grafting 4-vinylpyridine (PVA-g-PVP). The glucose oxidase entrapped in the composite matrix retained its bioactivity. Morphologies of the composite-modified electrode and the enzyme electrode were characterized with a scanning electron microscope. The dependence of the current responses on enzyme-loading and pH was studied. The response time of the biosensor was < 20 s and the linear range was up to 9 microM with a sensitivity of 405 nA/microM. The biosensor was stable for at least 1 month. In addition, the tetrathiafulvalene-mediated enzyme electrode was constructed for the decrease of detection potential and the effect of three common physiological sources that might interfere was also investigated.