Metal Free Polymer/Graphite Electrode-Ferricyanides Catholyte System for MFC with High Performance

A Microbial fuel cell(MFC)with metal free polymer/graphite electrodes(150 mm×150 mm)was constructed.The electrodes with flowing channels,which were different in roughness,were designed.No additional catalyst was coated on the electrode,therefore the MFC was cheaper and possessed good durability with high performance.The effect of roughness,K3Fe(CN)6 concentration and sprayed air on the performance of the constructed MFC was investigated.Results showed that the roughness of electrode can significantly affect the performance of MFC.The power density of MFC increased by 1.56 times owing to the arithmetic mean roughness which has increased by 1.41 times.With an increasing K3Fe(CN)6 concentration,the performance of MFC also improves.The MFC with K3Fe(CN)6 only(30 mM)showed the highest power density of 1260 mW/m2,which is by 21.4 times and 1.3 times higher than those of MFCs with spraying air only(59 mW/m2)and with K3Fe(CN)6+air(1005 mW/m2),respectively.This showed that the appropriate concentration of K3Fe(CN)6 can significantly improve the power density,while the air has a negative effect when it is sprayed onto K3Fe(CN)6 catholyte.A coulombic efficiency of 34.2%and an energy efficiency of 13.3%with a COD degradation rate of 73.5%were achieved with MFC using K3Fe(CN)6 only.The overpotentials of MFC were also calculated.It can be seen that both theηohmic andηconcentration were very low as compared to theηactivation,and theηconcentration can be ignored because its effect was less than 3 mV.The theoretical calculation suggested that with an increasing conversion rate of K3Fe(CN)6,the cathode potential decreased and reached 0.31 V at a conversion rate of 0.99.While the anode behaves differently for constant pH and changeable pH as the reaction progresses,which reveals that the buffer solution and removal of protons play an important role in maintaining the anode potential.

Removal of rubidium from brine by an integrated film of sulfonated polysulfone/graphene/potassium copper ferricyanide

A novel integrated film of sulfonated polysulfone/graphene/potassium copper ferricyanide(KCuFC/SPSG)was used for selectively extracting rubidium ion(Rb^(+))from brine.To form KCuFC/SPSG,the precursor film of sulfonated polysulfone/graphene(SPSG)was synthesized by phase conversion process,which was alternately immersed in 0.1 mol·L^(-1)CuSO_(4)/K_(4)[Fe(CN)_(6)]by in-situ adsorption coupled co-precipitation method.Various data such as nuclear magnetic resonance spectrometer,Fourier transform infrared spectroscope,X-ray photoelectron spectroscope,X-ray diffraction,scanning electron microscope,and energy dispersive spectroscopy all verified that abundant KCuFC were uniformly located on the film.The resulting KCuFC/SPSG was used in film separation system.As the solution was fed into the system,the Rb^(+)could be selectively adsorption by KCuFC/SPSG.After the saturation adsorption,0.5 mol·L^(-1)NH_(4)Cl/HCl was fed into the film cell,Rb^(+)could be quickly desorbed by ion-exchange between Rb^(+)and NH_(4)^(+)in the lattice of KCuFC.The purpose of separating and recovering Rb^(+)from the brine can be achieved after the repeated operation.The effects of pH,adsorption time,and interferential ions on the adsorption capacity of Rb^(+)were investigated by batch experiments.The adsorption behavior fits the pseudo-second order kinetic process,while KCuFC has a higher adsorption capacity(Langmuir maximum sorption 165.4 mg·g^(-1)).In addition,KCuFC/SPSG shows excellent selectivity for Rb^(+)even in complex brine systems.KCuFC/SPSG could maintain 93.5%extraction efficiency after five adsorption/desorption cycles.

Application of potassium ferricyanide in the spectrophotometric determination of captopril

A novel method for the determination of captopril by spectrophotometer is described in this paper. The experiment is based on the fact that Fe（Ⅲ） is reduced to Fe（Ⅱ） by captopril, then the in sire formed Fe（Ⅱ） reacts with potassium ferricyanide to give the soluble prussian blue at pH 4.00, and its maximal adsorption wavelength （λmax） is 735 nm. Good linear relationship is obtained between the absorbance and the concentration of captopril in the wide range of 0.05-20 μg/mL. The linear regression equation is A = -0.04314 ＋ 0.11423C （μg/mL） with a correlation coefficient R = 0.9998. The detection limit （3σ/k） is 0.04 μg/mL, the molar absorption coefficient is 2.5×10^4 L/mol cm. By mensurating the absorbance of soluble prussian blue, the indirect determination of captopril can be obtained. This method has been successfully applied to determination of captopril in pharmaceutical samples. Analytical results obtained are satisfactory.

Flow injection spectrophotometric determination of vitamin E in pharmaceuticals,milk powder and blood serum using potassium ferricyanide-Fe(Ⅲ) detection system

A simple and sensitive flow injection spectrophotometric method is reported for the determination of vitamin E using potassium ferricyanide-Fe(Ⅲ) detection system.In the presence of vitamin E,Fe(Ⅲ)/ferricyanide reduces.The in situ reduced ions are then reacted with unreduced portion of ferricyanide/Fe(Ⅲ) to make soluble Prussian blue,which is monitored at absorption wavelength of 735 nm.Linear calibration graph was obtained in the concentration range of 0.1-40μg mL^(-1).The relative standard deviations (n=4) were in the range of 1.1-3.6%,with limits of detection(3 s blank) of 0.04μg mL^(-1).The proposed method allowed 12 injections h^(-1).The method is applied to determine vitamin E in pharmaceuticals,infant milk and blood serum samples using hexane extraction with the recoveries in the range of 93±3 to 97.5±4%.The method is validated using certified reference materials SRM 968c for blood serum samples.

Silver dissolution in a novel leaching system: Reaction kinetics study

Effective silver recovery is usually restricted by either environmental pollution or high recovery costs. To tackle the issues, this study introduces a novel method for the effective recovery of silver by utilizing the alkaline sodium thiosulfate-potassium ferricyanide leaching system. The reaction kinetics of silver dissolution in this system was investigated via the rotating disk electrode technology. The influences of important parameters, including the rotation speed, sodium thiosulfate concentration, potassium ferricyanide concentration, and temperature, on the silver dissolution rate were systematically investigated. The activation energy was measured to be 17.96 kJ·mol^(-1) when the silver dissolution was controlled by a diffusion process. When the silver dissolution was in the region of mixed control, the reaction orders of ferricyanide and thiosulfate were found to be 0.57 and 0.19, respectively, and the reaction orders of ferricyanide and thiosulfate were 0.55 and 0.22, respectively, when the silver dissolution was controlled by surface reaction. This study has great potential for the development of an environmentally friendly silver recovery process from end-of-life products.

Flow-injection Determination of Cysteine,N-Acetyl Cysteine and Glutathione in Pharmaceuticals via Potassium Ferricyanide-Fe(Ⅲ) Spectrophotometric System

A simple flow injection spectrophotometric method is reported for the determination of cysteine,N-acetyl cysteine and glutathione based on the reduction of Fe（Ⅲ）/ferricyanide,the in situ reduced ions are reacted with unreduced portion of ferricyanide/Fe（Ⅲ） to form soluble Prussian blue,which is monitored at 735 nm.The calibration graphs are linear in the concentration ranges of（1―100）×10-6 mol/L for cysteine and N-acetyl cysteine,and（1―50）×10-6 mol/L for glutathione.The relative standard deviations of 1.8%,2.5% and 1.9% were found for eleven replicate analyses of 5×10-6 mol/L cysteine,N-acetyl cysteine and glutathione.The limits of detection（3σ blank） at 5×10-7 mol/L for cysteine,and 3×10-7 mol/L for N-acetyl cysteine and glutathione were obtained.The proposed method allowed 60 injections/h.The effects of common substances present in pharmaceuticals and human physiological fluids were examined.The method was applied to determining cysteine in pharmaceutical formulations with the recoveries in a range of 97% to 106% and the results obtained are agreed well with labeled values.

Electrocatalytic Determination of Dopamine in the Presence of Ascorbic Acid by Poly-L-proline and Ferricyanide Compound Film Modified Electrode

A novel biosensor was fabricated by the electrochemical polymerization of poly-L-proline（P-LP） and ferricyanide（FC） to form a compound film on a glassy carbon electrode（GCE）. The compound film modified electrode（P-LP/FC/GCE） shows electrocatalytic activity toward dopamine（DA） in a phosphate buffer solution（PBS, pH = 4.0） with a diminution of the overpotential and an increase in peak current. P-LP/FC/GCE was used to study the electrocatalytic oxidation of DA and ascorbic acid（AA） by means of cyclic voltammetry（CV）, differential pulse voltammetry（DPV） and amperometric i-t curve techniques. The overlapping anodic peaks of DA and AA were resolved into two well-defined voltammetric peaks in CV and DPV with the potential differences of about 200 and 225 mV, respectively. The peak current of DA is linearly change with the concentration of DA in a range of 1 × 10^-7 to 1.14 × 10^-4 mol/L with the correlation coefficient of 0.9997. The detection limit is 4.4~10-8 mol/L（S/N=3）. P-LP/FC/GCE exhibited an excellent selectivity, sensibility and stability for the determination of DA, and can be applied to the determination of dopamine injections with satisfied results.

Disposable Electrochemical Biosensor for Amperometric Measurement of β-hydroxybutyrate and Total Cholesterol

A new type of disposable thin-film amperometric biosensor has been developed for measurement ofβ-hydroxybutyrate and total cholesterol in serum.The biosensor consists of two plain gold electrodes mounted on a Polyethylene terephthalate (PET) substrate.The reagent solution contains bienzymes (cholesterol oxidase and cholesterol esterase for total cholesterol,β-hydroxybutyrate dehydrogenase and diaphorase forβ-hydroxybutyrate respectively) with mediator (ferricyanide) were absorption at the surface of electrodes coated by electrodepositing platinum black.The presence of the mediator lowers the applied potential and eliminates the interference from other oxidizable species enhancing the sensitivity and selectivity of the biosensor without modifying the dynamic parameters of the response.The enzymes stably retains in the matrices of platinum black film improving the performance of the mediated sensor.The linearity is observed in the concentration range from 1.0×10^(-4) to 1.0×10^(-2) mM and 1.0×10^(-4) mM to 4.99×10^(-3) mM with sensitivity of 1.958μA/mM and 2.447μA/mM respectively.The optimized biosensor exhibits excellent reproducibility and stability retaining more than 90% of its original activity over a period of one month.The simple operation of the biosensor mass-produced at low cost is expected to find clinical application and homecare.

A Green and Facile Solid-state Synthesis Method for the Preparation of Diazenecarboxamide Azo Compounds with Potassium Ferricyanide and Sodium Hydroxide System

Eleven new-typed azo compounds were synthesized in good yields by dehydrogenating the corresponding aryl substituted semicarbazides using potassium ferricyanide and sodium hydroxide system under solid-state conditions.

Studies on the Gold-Coated Electrode with Grid

Introduction Thin-layer spectroelectrochemical method has many unique advantages, therefore this method has been widely applied and developed. Recently light transparent thinlayer spectroelectrochemical cells with various types of structures have been reported at home and abroad with gold or platinum minigrids as the working electrode in most of

Potassium Ferricyanide Oxidative Cyclizationof Arylaldehyde with o-Phenylenediamine and o-Aminophenol to 2-Arylbenzimidazoles and 2-Arylbenzoxazoles

Some new benzimidazoles and benzoxazoles have been prepared under mild condition by oxidative cyclization of arylaldehyde witho-phenylenediamine ando-aminophenol using potassium ferricyanide as oxidant

Synthesis and Crystal Structure of a Novel Bimetallic Porphyrin Complex Salt {[MnTPP(CH_3OH)_2]_3Fe(CN)_6}·13H_2O

A novel bimetallic porphyrin complex salt, { [MnTPP（CHaOH）2]3Fe（CN）6}·13H2O （TPP = tetraphenylporphyrin）, has been synthesized and structurally characterized by X-ray diffraction analysis. The crystal is of trigonal, space group R-3 with a = b = 31.0618（10）, c = 11.8366（8）A, Z = 3, V = 9890.3（8）A^3, C144H134FeMn3N18O19, Mr = 2641.36, Dc = 1.330 g/cm^3, μ（MoKa） = 0.463 mm^-1, F（000） = 4131, R= 0.0525 and wR = 0.1382 for 3045 observed reflections （I 〉 2σ（I））. The title complex is composed of one [Fe（CN）6]^3- anion, three [MnTPP（CH3OH）2]^＋ cations and thirteen water molecules, which are connected by multiform hydrogen bonds leading to a 3D supramolecular network structure.

On the Criteria of Instability for Electrochemical Systems

Both cyclic-voltammetry-based and impedance-based experimental criteria thathave been developed recently for the oscil-latory electrochemical systems are critically appraisedwith two typical categories of oscillators. Consistent conclusions can be drawn by the two criteriafor the category of oscillators that involve the coupling of charge transfer mainly with surfacesteps (e.g. ad- and desorption) such as in the electrooxidation of C_1 organic molecules. Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the couplingof charge transfer mainly with mass transfer (e.g. diffusion and convection) such as in theFe(CN)_6^(3-) reduction accompanying periodic hydrogen evolution. The reason is that the negativeimpedance cannot include the feedback information of convection mass transfer induced by thehydrogen evolution. However, both positive and negative nonlinear feedbacks, i. e., thediffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)_6^(3-) surfaceconcentration, that coexist between the bistability, i. e., Fe(CN)_6^(3-) reduction with and withouthydrogen evolution at lower and higher potential sides respectively, are all reflected in thecrossed cyclic voltammo-gram (CCV). It can be concluded that the voltammetry-based criterion (intime domain) is more intuitive, less time-consuming and has a wider range of applications than theimpedance-based one (in frequency domain).

Ferricyanide-Promoted Oxidative Activation and Ligation of Protein Thioacids in Neutral Aqueous Media

Ferricyanide-promoted oxidative activation of Nacylatedα-aminothioacids for amide bond formation withα-aminonitriles was recently shown to be a plausible pathway for prebiotic peptide synthesis.Herein we describe the finding that by adding sodium azide and thiols,ferricyanide oxidation can elicit highly efficient and clean conversion of fully unprotected peptide or protein thioacids in neutral aqueous media to the corresponding thioesters.This transformation enables the development of ferricyanide-promoted thioacid-based native chemical ligation(NCL)as a new redox-based method for chemical protein synthesis,which does not need to change pH and is therefore operationally easy for ligation at small scales.The effectiveness of the ferricyanide-promoted thioacid-based NCL was illustrated by synthesis of an ISG15-modified MDA5 segment under nondenaturing conditions and synthesis of an acetylated ubiquitin(Ub)-modified histone H2A through an N-to-C sequential ligation.This work broadens the concept of on-demand oxidative activation strategy for protein ligation and provides a new useful supplement to the repertoire of methods for chemical protein synthesis,particularly for studies on proteins carrying Ub family modifications.