Electrochemical Studies for the Interaction of DNA with an Irreversible Redox Compound – Hoechst 33258

An electrochemical equation suitable for examining the interaction of irreversible redox compounds with DNA is established. According to the equation, diffusion coefficients of both free and binding compounds (D_f , D_b), binding constant (K) and binding site size (s) of compounds with DNA could be obtained simultaneously by nonlinear fit analysis of electrochemical data. Bis‐benzimidazole derivative (Hoechst 33258), as an irreversible redox compound, was investigated for its electrochemical behavior and the interaction with natural fish sperm DNA (fsDNA) using cyclic voltammetry, chronocoulometry, bulk electrolysis and scanning electrochemical microscope technique. A nonlinear fit analysis of the experimental data yielded: D_f=8.3×10^?5 cm² s^?1, D_b=6.0×10^?6 cm² s^?1, K=2.1×10⁸ cm³ mol^?1, s=3.9. The overall results suggest that Hoechst 33258 binds tightly to the minor groove of fsDNA and covers four base pairs.     

A High‐Performance Organic Field‐Effect Transistor Based on Platinum(II) Porphyrin: Peripheral Substituents on Porphyrin Ligand Significantly Affect Film Structure and Charge Mobility

Organic field‐effect transistors incorporating planar π‐conjugated metal‐free macrocycles and their metal derivatives are fabricated by vacuum deposition. The crystal structures of [H₂(OX)] (H₂OX=etioporphyrin‐I), [Cu(OX)], [Pt(OX)], and [Pt(TBP)] (H₂TBP=tetra‐(n‐butyl)porphyrin) as determined by single crystal X‐ray diffraction (XRD), reveal the absence of occluded solvent molecules. The field‐effect transistors (FETs) made from thin films of all these metal‐free macrocycles and their metal derivatives show a p‐type semiconductor behavior with a charge mobility (μ) ranging from 10^?6 to 10^?1 cm² V^?1 s^?1. Annealing the as‐deposited Pt(OX) film leads to the formation of a polycrystalline film that exhibits excellent overall charge transport properties with a charge mobility of up to 3.2×10^?1 cm² V^?1 s^?1, which is the best value reported for a metalloporphyrin. Compared with their metal derivatives, the field‐effect transistors made from thin films of metal‐free macrocycles (except tetra‐(n‐propyl)porphycene) have significantly lower μ values (3.0×10^?6–3.7×10^?5 cm² V^?1 s^?1).     

Electroless Deposition of Thionin onto Glassy Carbon Electrode Modified with Single Wall and Multiwall Carbon Nanotubes: Improvement of the Electrochemical Reversibility and Stability

A simple procedure was developed to prepare a glassy carbon electrode modified with carbon nanotubes (CNTs) and thionin. Abrasive immobilization of CNTs on a GC electrode was achieved by gently rubbing the electrode surface on a filter paper supporting carbon nanotubes, then immersing the GC/CNTs‐modified electrode into a thionin solution (electroless deposition) for a short period of time (5–50 s for MWCNTs and 5–120 s for SWCNTs ). Cyclic voltammograms of the resulting modified electrode show stable and a well defined redox couple with surface confined characteristic at wide pH range 2–12. The electrochemical reversibility and stability of modified electrode prepared with incorporation of thionin into CNTs film was compared with usual methods for attachment of thionin to electrode surfaces such as electropolymerization and adsorption on the surface of preanodized electrodes. The formal potential of redox couple (E°′) shifts linearly toward the negative direction with increasing solution pH. The surface coverage of thionin immobilized on CNTs glassy carbon electrode was approximately 1.95×10^?10 mol cm^?2 and 3.2×10^?10 mol cm^?2 for MWCNTs and SWCNTs, respectively. The transfer coefficient (α) was calculated to be 0.3 and 0.35 and heterogeneous electron transfer rate constants (K_s) were 65 s^?1 and 55 s^?1 for MWCNTs/thionin and SWCNTs/thionin‐modified GC electrodes, respectively. The results clearly show a great facilitation of the electron transfer between thionin and CNTs adsorbed on the electrode surface. Excellent electrochemical reversibility of redox couple, high stability, technically simple and possibility of preparation at short period of time are of great advantages of this procedure for modification of electrodes.     

Nanostructured Cobalt(II) Tetracarboxyphthalocyanine Complex Supported Within the MWCNT Frameworks: Electron Transport and Charge Storage Capabilities

The electrochemical redox properties of a surface‐confined thin solid film of nanostructured cobalt(II) tetracarboxyphthalocyanine integrated with multiwalled carbon nanotube (nanoCoTCPc/MWCNT) have been investigated. This novel nanoCoTCPc/MWCNT material was characterized using SEM, TEM, zeta analysis and electrochemical methods. The nanoCoTCPc/MWCNT nanohybrid material exhibited an extra‐ordinarily high conductivity (15 mS cm^?1), which is more than an order of magnitude greater than that of the MWCNT‐SO₃H (527 µS cm^?1) and three orders of a magnitude greater than the nanoCoTCPc (4.33 µS cm^?1). The heterogeneous electron transfer rate constant decreases as follows: nanoCoTCPc/MWCNT (k_app≈19.73×10^?3 cm s^?1)>MWCNT‐SO₃H (k_app≈11.63×10^?3 cm s^?1)>nanoCoTCPc (k_app≈1.09×10^?3 cm s^?1). The energy‐storage capability was typical of pseudocapacitive behaviour; at a current density of 10 µA cm^?2, the pseudocapacitance decreases as nanoCoTCPc/MWCNT (3.71×10^?4 F cm^?2)>nanoCoTCPc (2.57×10^?4 F cm^?2)>MWCNT‐SO₃H (2.28×10^?4 F cm^?2). The new nanoCoTCPc/MWCNT nanohybrid material promises to serve as a potential material for the fabrication of thin film electrocatalysts or energy‐storage devices.     

Electrooxidation and Amperometric Detection of Ascorbic Acid at GC Electrode Modified by Electropolymerization of N,N‐Dimethylaniline

The polymer film of N,N‐dimethylaniline (DMA) is deposited on the electrochemically pretreated glassy carbon (GC) electrode by continuous electrooxidation of the monomer. This poly N,N‐dimethylaniline (PDMA) film‐coated electrode can be used as an amperometric sensor of ascorbic acid (AA). The polymer film (thickness (?): 0.3±0.02 μm) having positive charge in its backbone attracts the anionic species AA. Thus, the anodic peak potential (350 mV vs. Ag|AgCl|NaCl_(sat)) for the oxidation of AA at the bare electrode is largely shifted to the negative value (150 mV) at this electrode. The PDMA film‐coated electrode is stable in acidic, alkaline and neutral media and can sense AA at different pH's. The diffusion coefficients of AA in solution (D) and in film (D_s) were estimated by rotating disk electrode voltammetry: D=(5.5±0.1)×10^?6 cm² s^?1 and D_s=(6.3±0.2)×10^?8, (6.0±0.2)×10^?8 and (4.7±0.2)×10^?8 cm² s^?1 for 0.5, 1.5 and 3.0 mM AA, respectively. A permeability of AA through the PDMA film was found to decrease with increasing the concentration of AA in the solution. In the chronoamperometry, the current response for the oxidation of AA at different times elapsed after potential‐step application is linearly increased with the increase in AA concentration in a wide range of its concentration from 25 μM to 1.65 mM. In the hydrodynamic amperometry, a successive addition of 10 μM AA caused the successive increase in current response with equal amplitude and the sensitivity was calculated as 0.178 μA cm^?2 μM^?1. So, the fouling of the electrode surface caused by the oxidized product of AA is markedly eliminated at this PDMA film‐coated electrode. A flow injection analysis based on the present electrode was performed to estimate the concentration of vitamin C in fruit juice.     

Direct electrochemistry and electrochemical biosensing of glucose oxidase based on CdSe@CdS quantum dots and MWNT-modified electrode

The direct electron transfer of glucose oxidase (GOx) was achieved based on the immobilization of CdSe@CdS quantum dots on glassy carbon electrode by multi-wall carbon nanotubes (MWNTs)-chitosan (Chit) film. The immobilized GOx displayed a pair of well-defined and reversible redox peaks with a formal potential (E ^θ’) of ?0.459 V (versus Ag/AgCl) in 0.1 M pH 7.0 phosphate buffer solution. The apparent heterogeneous electron transfer rate constants (k _s) of GOx confined in MWNTs-Chit/CdSe@CdS membrane were evaluated as 1.56 s^?1 according to Laviron's equation. The surface concentration (Γ*) of the electroactive GOx in the MWNTs-Chit film was estimated to be (6.52?±?0.01)?×?10^?11?mol?cm^?2. Meanwhile, the catalytic ability of GOx toward the oxidation of glucose was studied. Its apparent Michaelis–Menten constant for glucose was 0.46?±?0.01 mM, showing a good affinity. The linear range for glucose determination was from 1.6?×?10^?4 to 5.6?×?10^?3?M with a relatively high sensitivity of 31.13?±?0.02 μA?mM^?1?cm^?2 and a detection limit of 2.5?×?10^?5?M (S/N=3).     

Direct Electrochemistry and Electrocatalysis of the Hemoglobin Immobilized on Diazonium‐Functionalized Aligned Carbon Nanotubes Electrode

A simple and efficient electrochemical method is utilized to functionalize aligned carbon nanotubes (ACNTs) by the electrochemical reduction of 4‐carboxyphenyl diazonium salt. Thus hemoglobin (Hb) molecules were covalently immobilized on the diazonium‐ACNTs surface via carbodiimide chemistry. Direct electrochemistry and bioelectrocatalytic activity of the immobilized Hb were then investigated by cyclic voltammetry (CV) and amperometry techniques. It is showed that the Hb film on the diazonium‐ACNTs electrode had well‐defined redox peaks with a formal potential (E°) at ?312 mV (vs. Ag/AgCl), and the Hb‐ACNTs electrode displayed good electrocatalytic activity to H₂O₂ reduction. Owing to the high Hb covering on the ACNTs surface (Γ*=2.7×10^?9 mol cm^?2), the catalytic current were significantly improved when compared to the current measured at an Hb‐tangled carbon nanotubes electrode. The Hb‐ACNTs electrode exhibited high sensitivity, long‐term stability and wide concentration range from 40 μM to 3 mM for the amperometric detection of H₂O₂. The heterogeneous reaction rate constant (k_s) was 0.95±0.05 s^?1 and the apparent Michaelis–Menten constant (K was 0.15 mM.     

Electroconductive Hydrogels: Electrical and Electrochemical Properties of Polypyrrole‐Poly(HEMA) Composites

Composites of inherently conductive polypyrrole (PPy) within highly hydrophilic poly(2‐hydroxyethyl methacrylate)‐based hydrogels (p(HEMA)) have been fabricated and their electrochemical properties investigated. The electrochemical characteristics observed by cyclic voltammetry suggest less facile reduction of PPy within the composite hydrogel compared to electropolymerized PPy, as shown by the shift in the reduction peak potential from ?472 mV for electropolymerized polypyrrole to ?636 mV for the electroconductive composite gel. The network impedance magnitude for the electroconductive hydrogel remains quite low, ca. 100 Ω, even upon approach to DC, over all frequencies and at all offset potentials suggesting retained electronic (bipolaronic) conductivity within the composite. In contrast, sustained application of +0.7 V (vs. Ag/AgCl, 3 M Cl^?) for typically 100 min. (conditioning) to reduce the background amperometric current to <1.0 μA, resulted in complete loss of electroactivity. Nyquist plots suggest that sustained application of such a modest potential to the composite hydrogel results in impedance characteristics that resembles p(HEMA) without evidence of the conducting polymer component. PPy composite gels supported a larger ferrocene monocarboxylate diffusivity (D_appt=7.97×10^?5 cm² s^?1) compared to electropolymerized PPy (D_appt=5.56×10^?5 cm² s^?1), however a marked reduction in diffusivity (D_appt=1.01×10^?5 cm² s^?1) was observed with the conditioned hydrogel composite. Cyclic voltammograms in buffer containing H₂O₂ showed an absence of redox peaks for electrodes coated with PPy‐containing membranes, suggesting possible chemical oxidation of polypyrrole by the oxidant     

Direct Electrochemistry of Glucose Oxidase Immobilized on Titanium Carbide‐Au Nanoparticles‐Fullerene C60 Composite Film and Its Biosensing for Glucose

The direct electrochemistry of glucose oxidase (GOD) immobilized on the designed titanium carbide‐Au nanoparticles‐fullerene C₆₀ composite film modified glassy carbon electrode (TiC‐AuNPs‐C₆₀/GCE) and its biosensing for glucose were investigated. UV‐visible and Fourier‐transform infrared spectra of the resulting GOD/TiC‐AuNPs‐C₆₀ composite film suggested that the immobilized GOD retained its original structure. The direct electron transfer behaviors of immobilized GOD at the GOD/TiC‐AuNPs‐C₆₀/GCE were investigated by cyclic voltammetry in which a pair of well‐defined, quasi‐reversible redox peaks with the formal potential (E^0′) of ‐0.484 V (vs. SCE) in phosphate buffer solution (0.05 M, pH 7.0) at the scan rate of 100 mV·s^?1 were obtained. The proposed GOD modified electrode exhibited an excellent electrocatalytic activity to the reduction of glucose, and the currents of glucose reduction peak were linearly related to glucose concentration in a wider linearity range from 5.0 × 10^?6 to 1.6 × 10^?4 M with a correlation coefficient of 0.9965 and a detection limit of 2.0 × 10^?6 M (S/N = 3). The sensitivity and the apparent Michaelis‐Menten constant (K_M^app) were determined to be 149.3 μA·mM^?1·cm^?2 and 6.2 × 10^?5 M, respectively. Thus, the protocol will have potential application in studying the electron transfer of enzyme and the design of novel electrochemical biosensors.     

Solid state voltammetric characterization of iron hexacyanoferrate encapsulated in silica

We describe a sol-gel approach by which iron hexacyanoferrate is immobilized in silica in a manner suited to investigation by electrochemistry in the absence of a contacting liquid phase. Such physicochemical parameters as concentration of redox sites (C _o) and apparent (effective) diffusion coefficient (D _app) are estimated by performing cyclic voltammetric and potential step experiments in two time regimes, which are characterized by linear and spherical diffusional patterns, respectively. Values of D _app and C _o thereby obtained are 2.0 × 10⁻⁶ cm² s⁻¹ and 1.4 × 10⁻² mol dm⁻³. The D _app value is larger than expected for a typical solid redox-conducting material. Analogous measurements done in iron(III) hexacyanoferrate(III) solutions of comparable concentrations, 1.0 × 10⁻² and 5.0 × 10⁻³ mol dm⁻³, yield D _app on the level of 5–6 × 10⁻⁶ cm² s⁻¹. Thus, the dynamics of charge propagation in this sol-gel material is almost as high as in the liquid phase. The residual water in the silica, along with the pore structure, are important to the overall mechanism of charge transport, which apparently is limited by physical diffusion rather than electron self-exchange. Under conditions of a solid state voltammetric experiment which utilizes an ultramicroelectrode, encapsulated iron hexacyanoferrate redox centers seem to be in the dispersed colloidal state rather than in a form of the rigid polymeric film. Received: 8 April 1999 / Accepted: 13 August 1999     

Electrochemical DNA impedance biosensor for the detection of DNA hybridization with polymeric film, single walled carbon nanotubes modified glassy carbon electrode

In this work, we report the fabrication of a sensitive electrochemical DNA impedance biosensor for the detection of sequence-specific target DNA. p-Aminobenzoic acid was first immobilized on the surface of the electrode modified with single walled carbon nanotubes with carboxylic acid groups (SWCNTs) by cyclic voltammetry (CV). A single-stranded DNA probe with a NH₂ group at the end (H₂N-ssDNA) was then covalently immobilized on the surface of polymeric film at room temperature. The impedance measurement was performed in a solution containing 5 mM K₃[Fe(CN)₆]/K₄[Fe(CN)₆]. The change of interfacial charge transfer resistance (R _CT) was confirmed the hybrid formation. The difference of R _CT was linear with the logarithm of complementary oligonucleotides concentrations in the range of 1.0 × 10^?12 to 1.0 × 10^?7 M, with a detection limit of 3.5 × 10^?13 M (S/N = 3).     

Direct Voltammetry of Copper,Zinc‐Superoxide Dismutase Immobilized onto Electrodeposited Nickel Oxide Nanoparticles: Fabrication of Amperometric Superoxide Biosensor

Direct electron transfer of immobilized copper, zinc‐superoxide dismutase (SOD) onto electrodeposited nickel‐oxide (NiOx) nanoparticle modified glassy carbon (GC) electrode displays a well defined redox process with formal potential of ?0.03 V in pH 7.4. Cyclic voltammetry was used for deposition of (NiOx) nanoparticles and immobilization of SOD onto GC electrode. The surface coverage (Γ) and heterogeneous electron transfer rate constant (k_s) of immobilized SOD are 1.75×10^?11 mol cm^?2 and 7.5±0.5 s^?1, respectively. The biosensor shows a fast amperometric response (3 s) toward superoxide at a wide concentration range from 10 µM to 0.25 mM with sensitivity of 13.40 nA µM^?1 cm^?2 and 12.40 nA µM^?1 cm^?2, detection limit of 2.66 and 3.1 µM based on anodically and cathodically detection. This biosensor exhibits excellent stability, reproducibility and long life time.     

The relaxation of HCl(ν = 1) and DCl(ν = 1) by O atoms between 196 and 400 K

The rates of relaxation of HCl(ν = 1) and DCl(ν = 1) by atomic oxygen have been determined between 196 and 400 K using the laser induced vibrational fluorescence method. The values of the rate constants, κ_1,H and κ_1,D, can be matched quite well by Arrhenius expressions: κ_1,H = 6.2 × 10^?12 exp (?1.0₅ kcal mole^?1/RT) cm³ molecule^?1 s^?1 and κ_1,D = 2.9 × 10^?12 exp (?0.5 kcal mole^?1/RT) cm³ molecule^?1 s^?1. The most likely explanation of the absolute and relative magnitudes of these rate constants appears to be that relaxation occurs as a result of non-adiabatic vibronic transitions during collisions.     

Sensitive amperometric pyridoxine sensor based on self‐assembled Prussian blue nanoparticle‐modified poly(o‐phenylenediamine)/glassy carbon electrode

Prussian blue nanoparticles (PBNPs) were prepared by a self‐assembly process on a glassy carbon electrode (GCE) modified with poly(o‐phenylenediamine) (PoPD) film. The stepwise fabrication process of PBNP‐modified PoPD/GCE was characterized using scanning electron microscopy and electrochemical impedance spectroscopy. The prepared PBNPs showed an average size of 70 nm and a homogeneous distribution on the surface of the modified electrode. The PBNPs/PoPD/GCE showed electrocatalytic activity towards the oxidation of pyridoxine (PN) and was used as an amperometric sensor. The modified electrode exhibited a linear response for PN oxidation over the concentration range 3–38.5 μM with a detection limit of ca 6.10 × 10^?7 M (S/N = 3) and sensitivity of 2.79936 × 10³ mA M^?1 cm^?2 using an amperometric method. The mechanism and kinetics of the catalytic oxidation reaction of PN were investigated using cyclic voltammetry and chronoamperometry. The values of α, k_cat and D were estimated as 0.36, 1.089 × 10² M^?1 s^?1 and 8.9 × 10^?5 cm² s^?1, respectively. This sensor also exhibited good anti‐interference and selectivity. Copyright © 2016 John Wiley & Sons, Ltd.     

Determination of Reduced Nicotinamide Adenine Dinucleotide Based on Immobilization of Tris(2,2′‐bipyridyl) Ruthenium(II) in Multiwall Carbon Nanotubes/Nafion Composite Membrane

Abstract

An electrochemiluminescence (ECL) method for reduced nicotinamide adenine dinucleotide (NADH) was proposed by immobilizing tris(2,2′‐bipyridyl) ruthenium(II) (Ru(bpy)₃ ²⁺) in multiwall carbon nanotubes (MWCNTs)/Nafion composite membrane that was formed on glassy carbon electrode surface. The electrochemical and ECL behaviors of the immobilized Ru(bpy)₃ ²⁺ were investigated. The cyclic votammogram of the modified electrode in pH 7.0 phosphate buffer solution showed a couple of redox peaks at +1190 and +1060 mV at 100 mV/s. The composite film had a more open structure and a large surface area allowing faster diffusion of Ru(bpy)₃ ²⁺. The presence of MWCNTs resulted in the improved ECL sensitivity and longer‐term stability of the modified electrode. The modified electrode showed a linear response to NADH in the concentration range of 1.0×10^?6 to 1.6×10^?5 M with a detection limit of 8.2×10^?7 M.     

Fabrication of Glucose Biosensor Based on Encapsulation of Glucose‐Oxidase on Sol‐Gel Composite at the Surface of Glassy Carbon Electrode Modified with Carbon Nanotubes and Celestine Blue

A simple procedure was developed to prepare a glassy carbon electrode modified with multi walled carbon nanotubes (MWCNTs) and Celestin blue. Cyclic voltammograms of the modified electrode show stable and a well defined redox couple with surface confined characteristic at wide pH range (2–12). The formal potential of redox couple (E′) shifts linearly toward the negative direction with increasing solution pH. The surface coverage of Celestine blue immobilized on CNTs glassy carbon electrode was approximately 1.95×10^?10 mol cm^?2. The charge transfer coefficient (α) and heterogeneous electron transfer rate constants (k_s) for GC/MWCNTs/Celestine blue were 0.43 and 1.26 s^?1, respectively. The modified electrode show strong catalytic effect for reduction of hydrogen peroxide and oxygen at reduced overpotential. The glucose biosensor was fabricated by covering a thin film of sol‐gel composite containing glucose oxides (GOx) on the surface of Celestine blue /MWCNTs modified GC electrode. The biosensor can be used successfully for selective detection of glucose based on the decreasing of cathodic peak current of oxygen. The detection limit, sensitivity and liner calibration rang were 0.3 μM, 18.3 μA/mM and 10 μM–6.0 mM, respectively. The accuracy of the biosensor for glucose detection was evaluated by detection of glucose in a serum sample, using standard addition protocol. In addition biosensor can reach 90% of steady currents in about 3.0 sec and interference effect of the electroactive existing species (ascorbic acid–uric acid and acetaminophen) was eliminated. Furthermore, the apparent Michaelis–Menten constant 2.4 mM, of GOx on the nano composite exhibits excellent bioelectrocatalytic activity of immobilized enzyme toward glucose oxidation. Excellent electrochemical reversibility of redox couple, high stability, technically simple and possibility of preparation at short period of time are of great advantages of this procedure for modification of glucose biosensor.     

Electrochemical Behavior and Determination of L‐Tyrosine at Single‐walled Carbon Nanotubes Modified Glassy Carbon Electrode

Based on single‐walled carbon nanotubes (SWCNTs) modified glassy carbon electrode (GCE/SWCNTs), a novel method was presented for the determination of L ‐tyrosine. The GCE/SWCNTs exhibited remarkable catalytic and enhanced effects on the oxidation of L ‐tyrosine. In 0.10 mol/L citric acid‐sodium citrate buffer solution, the oxidation potential of L ‐tyrosine shifted negatively from +1.23 V at bare GCE to +0.76 V at GCE/SWCNTs. Under the optimized experimental conditions, the linear range of the modified electrode to the concentration of L ‐tyrosine was 5.0×10^?6–2.0×10^?5 mol/L (R₁=0.9952) and 2.7×10^?5–2.6×10^?4 mol/L (R₂=0.9998) with a detection limit of 9.3×10^?8 mol/L. The kinetic parameters such as α (charge transfer coefficient) and D (diffusion coefficient) were evaluated to be 0.66, 9.82×10^?5 cm² s^?1, respectively. And the electrochemical mechanism of L ‐tyrosine was also discussed.     

Direct Electrochemistry and Electrocatalysis of Hemoglobin Based on Nafion‐Room Temperature Ionic Liquids‐Multiwalled Carbon Nanotubes Composite Film

A robust and effective composite film combined the benefits of Nafion, room temperature ionic liquid (RTIL) and multi‐wall carbon nanotubes (MWNTs) was prepared. Hemoglobin (Hb) was successfully immobilized on glassy carbon electrode surface by entrapping in the composite film. Direct electrochemistry and electrocatalysis of immobilized Hb were investigated in detail. A pair of well‐defined and quasi‐reversible redox peaks of Hb was obtained in 0.10 mol·L^?1 pH 7.0 phosphate buffer solution (PBS), indicating that the Nafion‐RTIL‐MWNTs film showed an obvious promotion for the direct electron transfer between Hb and the underlying electrode. The immobilized Hb exhibited an excellent electrocatalytic activity towards the reduction of H₂O₂. The catalysis current was linear to H₂O₂ concentration in the range of 2.0×10^?6 to 2.5×10^?4 mol·L^?1, with a detection limit of 8.0×10^?7 mol·L^?1 (S/N=3). The apparent Michaelis‐Menten constant (K_m^app) was calculated to be 0.34 mmol·L^?1. Moreover, the modified electrode displayed a good stability and reproducibility. Based on the composite film, a third‐generation reagentless biosensor could be constructed for the determination of H₂O₂.     

Electrochemical Investigation of Cytochrome c Immobilized onto Self‐Assembled Monolayer of Captopril

The electrochemical behavior of cytochrome c (cyt‐c) that was electrostatically immobilized onto a self‐assembled monolayer (SAM) of captopril (capt) on a gold electrode has been investigated. Cyclic voltammetry, scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy were employed to evaluate the blocking property of the capt SAM. SECM was used to measure the bimolecular electron transfer (ET) kinetics (k_BI) between a solution‐based redox probe and the immobilized protein. In addition, the tunneling ET between the immobilized protein and the underlying gold electrode was calculated. A k_BI value of (5.0±0.6)×10⁸ mol^?1 cm³ s^?1 for the bimolecular ET and a standard tunneling rate constant (k⁰) of 46.4±0.2 s^?1 for the tunneling ET have been obtained.     

Adsorption rate of Reactive Black 5 on chitosan based materials: geometry and swelling effects

The overall adsorption rate of Reactive Black 5 dye (RB5) on chitosan based materials was elucidated using diffusional models. Fundamental aspects, such as, geometry of the adsorbents and swelling effects were considered. Chitosan based materials (powder and film) were prepared from shrimp wastes and characterized regarding to the fundamental features for adsorption. Experimental decay curves were obtained under different conditions of stirring rate and initial dye concentration. The data were modeled according to the external mass transfer and diffusional models. The k_L (external mass transfer coefficient), D_ep (effective pore diffusion coefficient) and D_s (surface diffusion coefficient) values were estimated. For both adsorbents, it was found that the surface diffusion was the intraparticle diffusion mechanism governing the adsorption rate of RB5, since its contribution was higher than 92 % regardless the position and time. The D_s values ranged from 2.85 × 10^?11 to 5.78 × 10^?11 for chitosan powder and from 4.15 × 10^?11 to 12.12 × 10^?11 cm² s^?1 for chitosan films. The RB5 adsorption was faster when chitosan powder was used, mainly at higher stirring rates and initial dye concentrations. The swelling effect was most pronounced for the chitosan films, where, provided an increase of about 65 times in the D_s value.