Platinum-macrocycle co-catalysts for electro-oxidation of formic acid

In this paper, it was found that the electrocatalytic activity of a Pt electrode for the electro-oxidation of formic acid could be dramatically enhanced with the modification of macrocycle compounds, such as iron-tetrasulfophthalocyanine (FeTSPc). The electro-oxidation of formic acid on a modified Pt electrode with FeTSPc occurs mainly through a direct pathway. A series of macrocycle compounds were also investigated as modifiers and exhibited a promotion effect similar to the Pt electrode.

Methylene blue as an indicator for sensitive electrochemical detection of adenosine based on aptamer switch

In this paper, a simple, label-free and regenerative method was proposed to study the interaction between aptamer and small molecule by using methylene blue (MB+) as an electrochemical indicator. A thiolated capture probe containing twelve bases was firstly self-assembled on gold electrode by gold-sulfur affinity. Aptamer probe containing thirty two bases, which was designed to hybridize with capture DNA sequence and specifically recognize adenosine, was then immobilized on the electrode surface by hybridization reaction. MB+ was abundantly adsorbed on the aptamer probe by the specific interaction between MB+ and guanine base in aptamer probe. MB+-anchored aptamer probe can be forced to dissociate from the sensing interface after adenosine triggered structure switching of the aptamer. The peak current of MB+ linearly decreased with the concentration of adenosine over a range of 2 x 10 (8)- x 10 (6) M with a detection limit of 1 x 10 (8) M. In addition, we examined the selectivity of this electrochemical biosensor for cytidine, uridine and guanosine that belonged to the nucleosides family and possessed 1 similar structure with adenosine.

Solid-state electrochemiluminescence sensor based on the Nafion/poly(sodium 4-styrene sulfonate) composite film

An effective electrochemiluminescence (ECL) sensor based on Nafion/poly(sodium 4-styrene sulfonate) (PSS) composite film-modified ITO electrode was developed. The Nafion/PSS/Ru composite film was characterized by atomic force microscopy, UV-vis absorbance spectroscopy and electrochemical experiments. The Nafion/PSS composite film could effectively immobilize tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) via ion-exchange and electrostatic interaction. The ECL behavior of Ru(bpy)(3)(2+) immobilized in Nafion/PSS composite film was investigated using tripropylamine (TPA) as an analyte. The detection limit (S/N = 3) for TPA at the Nafion/PSS/Ru composite-modified electrode was estimated to be 3.0 nM, which is 3 orders of magnitude lower than that obtained at the Nafion/Ru modified electrode. The Nafion/PSS/Ru composite film-modified indium tin oxide (ITO) electrode also exhibited good ECL stability. In addition, this kind of immobilization approach was simple, effective, and timesaving.

Interaction Between Tripeptide Gly-Gly-His and Cu2+ Probed by Microcantilevers

Gly-Gly-His tripeptide modified microcantilever was developed by carbodiimide attachment of the Gly-Gly-His tripeptide onto a 3-mercaptopropionic acid(MPA) modified gold surface. The interaction of peptide with Cu2+ ion was studied. At a relative high concentration of Cu2+, the cantilever bent toward the gold side initially as the N atom of imidazole ring and carboxyl group in different peptide coordinate with Cu2+, which results in a tensile surface stress. And then the reversed deflection of microcantilever was observed, which implies that the peptide-Cu2+ complex are formed with conformation transition. In another case, i.e., at a relative low concentration Of Cu2+, only the process of conformation transition was observed due to the coordination mode can not be formed initially. The influences of pH and salt concentration of the test solution on the performance of the sensor were studied. The results show that the maximum deflection was obtained at pH 7 and the bonding Of Cu2+ to the Gly-Gly-His tripeptide was inhibited due to the formation Of CuClx2-x.

Interaction between alpha-actinin and negatively charged lipids membrane investigated by surface plasmon resonance and electrochemical methods

alpha-Actinin has been shown to be capable of interacting with some special membrane phospholipids directly, which is important for its function. In this study, hybrid bilayer membranes composed of negatively charged lipids are constructed on the surface plasmon resonance gold substrate and on the gold electrode, respectively, and the interaction between alpha-actinin and negatively charged lipids membrane is investigated by surface plasmon resonance, cyclic voltammetry and electrochemical impedance spectroscopy methods. alpha-Actinin is proved to be able to interact with the negatively charged lipids membrane directly. It can also insert at least partly into the membrane or lead to some defect or lesion in the membrane, which increase the permeability of the membrane. This study would bring some insight on the interaction between the alpha-actinin and the cell membranes in vivo.

Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in Nafion-RTIL composite film

The composite film based on Nafion and hydrophobic room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim] PF6) was explored. Here, Nafion was used as a binder to form Nafion-ionic liquids composite film and help [bmim] PF6 effectively adhered on glassy carbon (GC) electrode. X-ray photoelectron spectroscopy (XPS), cyclic voltammtery (CV) and electrochemical impedance spectroscopy (EIS) were used to characterize this composite film, showing that the composite film can effectively adhere on the GC electrode surface through Nafion interacting with [bmim] PF6 and GC electrode. Meanwhile, doping [bmim] PF6 in Nafion can also effectively reduce the electron transfer resistance of Nafion. The composite film can be readily used as an immobilization matrix to entrap horseradish peroxidase (HRP). A pair of well-defined redox peaks of HRP was obtained at the HRP/Nafion[bmim] PF6 composite film-modified GC electrode through direct electron transfer between the protein and the underlying electrode. HRP can still retain its biological activity and enhance electrochemical reduction towards O-2 and H2O2. It is expected that this composite film may find more potential applications in biosensors and biocatalysis.

Nanoelectrode ensembles based on semi-interpenetrating network of carbon nanotubes

A method for preparing nanoelectrode ensembles based on semi-interpenetrating network (SIN) of multi-walled carbon nanotubes (MWNTs) on gold electrode through phase-separation method is initially proposed. Individual nanoelectrode owns irregular three-dimensional MWNTs networks, which is denoted as SIN-MWNTs. On the as-prepared SIN-MWNTs nanoelectrode ensembles, the assembled MWNTs clusters in nanoscale serve as individual nanoelectrode and the electroinactive lipid networks located on the top of alkanethiol monolayer are used as a shielding layer. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), tapping-mode atomic force microscopy (TM-AFM) and scanning electron microscopy (SEM) were used to characterize the as-prepared SIN-MWNT nanoelectrode ensembles. Experimental results indicate that the well-defined nanoelectrode ensembles were prepared through self-assembly technology. Meantime, sigmoid curves in a wide scanning range can be obtained in CV experiments. This study may pave the way for the construction of truly nanoscopic nanoelectrode arrays by bottom-up strategy.

Room temperature ionic liquid doped DNA network immobilized horseradish peroxidase biosensor for amperometric determination of hydrogen peroxide

A novel electrochemical H2O2 biosensor was constructed by embedding horseradish peroxide (HRP) in a 1-butyl-3-methylimidazolium tetrafluoroborate doped DNA network casting on a gold electrode. The HRP entrapped in the composite system displayed good electrocatalytic response to the reduction of H2O2. The composite system could provide both a biocompatible microenvironment for enzymes to keep their good bioactivity and an effective pathway of electron transfer between the redox center of enzymes, H2O2 and the electrode surface. Voltammetric and time-based amperometric techniques were applied to characterize the properties of the biosensor. The effects of pH and potential on the amperometric response to H2O2 were studied. The biosensor can achieve 95% of the steady-state current within 2 s response to H2O2. The detection limit of the biosensor was 3.5 mu M, and linear range was from 0.01 to 7.4 mM. Moreover, the biosensor exhibited good sensitivity and stability. The film can also be readily used as an immobilization matrix to entrap other enzymes to prepare other similar biosensors.

Effect of La3+ on structure and electrochemical reaction of microperoxidase-11 in imitated physiological solution

In this paper, the interaction mechanism between La3+ and microperoxidase-11 (MP-11) in the imitated physiological solution was investigated with the electrochemical and spectroscopic methods. It was found that when the molar ratio of La3+, and MP-11 is low, such as 2, La3+ can coordinate with oxygen in the propionic acid group of the heme group in the MP-11 molecule, forming the La-MP-11 complexes and leading to the increase in the non-planarity of the porphyrin cycle in the heme group and then the increase in the extent of exposure of the electrochemically active center, Fe(I I I) in the porphyrin cycle of the heme group. The increase in the extent of exposure of the electrochemically active center, Fe(III) in the porphyrin cycle of the heme group would increase the reversibility of the electrochemical reaction of the La-MP-11 complexes and its electrocatalytic activity for the reduction of H2O2. The results of the chromatographic analysis demonstrated that the average molar ratio of La3+ and MP-11 in the La-MP-11 complexes is 1.62.When the molar ratio of La3+ and MP-11 is high, such as 3, La3+ would shear some amino acid residues of the peptide of MP-11. Therefore, many La3+ ions can bind to the oxygen- and/or nitrogen-containing groups in the sheared amino acid residues except coordinating with the sheared and non-sheared MP-11 molecules.

Interaction between La3+ and MP-11 in the physiological solution

In this paper, the interaction between La3+ and microperoxidase-11 (MP-11) in the imitated physiological solution was investigated with the electrochemical method, circular dichroism (CD) and ultraviolet-visible (UV-vis) absorption spectroscopy. It was found that the interaction ways between La3+ and MP-11 are different with increasing the molar ratio of La3+ and MP-11. When the molar ratio of La3+ and MP-11 is less than 2, La3+ mainly interacts with the metacetonic acid group of the heme group in the MP-11 molecules, causing the increase in the non-planarity of the porphyrin cycle in the heme group and the decrease in the content of the random coil conformation of MP-11. These structural changes would increase the exposure extent of the electrochemical active center of MP-11 and thus, La3+ can promote the electrochemical reaction of MP-11 and its electrocatalytic activity for the reduction of H2O2 at the glassy carbon (GC) electrode. However, when the molar ratio of La3+ and MP-11 is larger than 3, except binding to the carbonyl oxygen of the metacetonic acid group in the heme group, La3+ interacts also with the oxygen-containing groups of the amides in the polypeptide chains of the MP-11 molecules, leading to the increase in the contents of the random coil conformation in the peptide of the MP-11 molecule, comparing with that for the molar ratio of less than 2.

The electrocatalytic oxidation of ascorbic acid on polyaniline film synthesized in the presence of camphorsulfonic acid

Polyaniline-camphorsulfonic acid (PAN-CSA) composite film on platinum electrode surface has been synthesized via the electrochemical polymerization of aniline in the presence of camphorsulfonic acid (CSA). It was found that the doping of polyaniline (PAN) with CSA extends the electroactivity of PAN in neutral and even in alkaline media. The PAN-CSA composite film coated platinum electrodes are shown to be good electrocatalytic surfaces for the oxidation of ascorbic acid (AA) in phosphate buffer solution (PBS) of pH 7.0. The anodic peak potential of AA shifts from 0.63 V at the bare platinum electrode to 0.34 V at the PAN-CSA composite modified platinum electrode with a greatly enhanced current response. A linear calibration graph is obtained over the AA concentration range of 5-50 mM using cyclic voltammetry. The kinetics of the catalytic reaction are investigated using rotating disk electrode voltammetry and chronoamperometry. The results are explained using the theory of electrocatalytic reactions at chemically modified electrodes. The PAN-CSA composite on the electrode surface shows good reproducibility and stability.

Facile preparation of amperometric laccase biosensor with multifunction based on the matrix of carbon nanotubes-chitosan composite

The carbon nanotubes-chitosan (CNTs-CS) composite provides a suitable biosensing matrix due to its good conductivity, high stability, and good biocompatibility. Enzymes can be firmly incorporated into the matrix without the aid of other cross-linking reagents. The composite is easy to form insoluble film in solution above pH 6.3. Based on this, a facilely fabricated amperometric biosensor by entrapping laccase into the CNTs-CS composite film has been developed. At pH 6.0, the fungi laccase incorporated into the composite film remains better catalytic activity than that dissolved in solution. The system is in favor of the accessibility of substrate to the active site of laccase, thus the affinity to substrates is improved greatly, such as 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) diammonium salt (ABTS), catechol, and 0, with K. values of 19.86 mu M, 9.43 mu M, and 3.22 mM, respectively. The major advantages of the as-prepared biosensor are: detecting different substrates (ABTS, catechol, and 02), possessing high affinity and sensitivity, durable long-term stability, and facile preparation procedure. On the other hand, the system can be applied in fabrication of biofuel cells as the cathodic catalysts based on its good electrocatalysis for oxygen reduction.

Composite film of carbon nanotubes and chitosan for preparation of amperometric hydrogen peroxide biosensor

A new amperometric biosensor for hydrogen peroxide was developed based on cross-linking horseradish peroxidase (HRP) by glutaraldehyde with multiwall carbon nanotubes/chitosan (MWNTs/chitosan) composite film coated on a glassy carbon electrode. MWNTs were firstly dissolved in a chitosan solution. Then the morphology of MWNTs/chitosan composite film was characterized by field-emission scanning electron microscopy. The results showed that MWNTs were well soluble in chitosan and robust films could be formed on the surface. HRP was cross-linked by glutaraldehyde with MWNTs/chitosan film to prepare a hydrogen peroxide biosensor. The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for H2O2 in the absence of a mediator. The linear range of detection towards H2O2 (applied potential: -0.2 V) was from 1.67 x 10(-5) to 7.40 x 10(-4) M with correction coefficient of 0.998. The biosensor had good repeatability and stability for the determination of H2O2. There were no interferences from ascorbic acid, glucose, citrate acid and lactic acid.

Electrochemical and spectroscopic study on the interaction of cytochrome c with anionic lipid vesicles

The structure and the electron-transfer of cytochrome c binding on the anionic lipid vesicles were analyzed by electrochemical and various spectroscopic methods. It was found that upon binding to anionic lipid membrane, the formal potential of. cytochrome c shifted 30 mV negatively indicating an eager redox interaction than that in its native state. This is due to the local alteration of the coordination and the heme crevice. The structural Perturbation in which a molten globule-like state is formed during binding to anionic lipid vesicles is more important. This study may help to understand the mechanism of the electron-transfer reactions of cytochrome c at the mitochondrial membrane.

Metal-containing molecular wires and their electron transportation properties

Metal-containing conjugated bisthioester 1 was synthesized. It was fabricated into "gold electrode - molecular wires monolayers - gold nanoparticles" junction using self-assembly and nanoparticles deposition techniques. The junction is suitable for investigating the electron transportation property of molecular wires.