Electrochemical quartz crystal nanobalance (EQCN) studies of the adsorption behaviour of an enzyme, mandelate racemase, and its substrate, mandelic acid, on Pt

The adsorption behaviour of the enzyme, mandelate racemase (MR), and its substrate, (S)-mandelic acid (MA), was studied at a polycrystalline Pt surface in pH 7.4 phosphate buffer at 294 K using the electrochemical quartz crystal nanobalance (EQCN) technique of simultaneous cyclic voltammetry (CV) and frequency measurements. It was shown that the EQCN frequency measurements did not directly monitor the molar mass of the adsorbed protein at anodic potentials, but instead measured changes in the surface oxide in the absence and presence of adsorbed protein. However, at a potential characteristic of the double layer for platinum, EQCN frequency measurements gave a measure of the extent of solvent displacement by the adsorbed protein. The adsorption process was modelled using the Langmuir adsorption isotherm. The values for the Gibbs energy of adsorption, ΔG_ADS, obtained with these EQCN frequency measurements gave excellent agreement within experimental uncertainty with those obtained from the simultaneous CV measurements for both the enzyme and substrate, and showed the enzyme to have a greater affinity for the surface than the substrate molecule. The maximum surface concentrations from CV and EQCN frequency measurements gave excellent agreement for the two techniques and showed MA to be adsorbed in a tilted orientation with monolayer coverage. On the other hand, the surface concentrations showed the presence of ∼2.5 monolayers of enzyme from charge transfer CV measurements, while the frequency results showed the presence of a densely packed monolayer from the “footprint” of solvent displacement by the adsorbed enzyme molecules on the electrode surface. The two techniques provide valuable complementary information on the interfacial behaviour of molecules.     

Nanogravimetric study of the complex voltammetric response in the electro-oxidation of methanol on platinum

Instead of a time-invariant voltammetric profile, many electrochemical systems display a cycle-dependent current-potential response. This phenomenon has been referred to as complex voltammetric response and it has been observed during the electro-oxidation of several molecules such as methanol, ethanol, propanol and hydrogen. There are currently two explanations for the surface mechanism underlying this behavior. In one scenario, the complex voltammogram would result from the specific kinetic pathway taken during the forward sweep. In the other explanation, the phenomenon is discussed in terms of the interplay among the surface roughening and subsequent relaxation, and the ohmic drop coupled to a negative differential resistance. We report in this paper a nanogravimetric investigation of the complex voltammetric response in the electro-oxidation of methanol on platinum electrode in both acidic and alkaline media. Different periodic patterns composed of intercalated small and large hysteresis cycles were observed as a function of the applied voltage and the series resistance between the working electrode and the potentiostat. Independently, nanogravimetric results indicated no detectable difference in the delta-frequency versus voltage profile between small and large hysteresis cycles. These findings were interpreted as experimental evidence of the secondary, if any, role played by the very electrochemical reaction on the emergence of complex voltammetric response.     

Electrochemical quartz crystal microbalance study of formation and redox transformations of poly(diphenylamine)

The electropolymerization of diphenylamine (DPA) dissolved in 2 mol dm⁻³ H₂SO₄ has been studied on a gold electrode by cyclic electrochemical quartz crystal microbalance measurements. Similar experiments have been accomplished with DPA microcrystals attached to a gold electrode, in the presence of aqueous acidic media. In both cases the redox transformations of the poly(diphenylamine) films formed on Au have been investigated in solutions of different pHs. The cyclic voltammograms and the mass changes refer to two closely spaced redox reactions resulting in the formation of cation radicals and dications, respectively. The irregular, broad shape of the voltammetric waves may be explained by presence of other electrochemically active sites beside the linear diphenylbenzidine structure. The results indicate a pH and potential-dependent relative contribution of anions and hydrogen ions to the overall ion exchange process. The expulsion of protons is the predominant ion transport process at the beginning of the oxidation and the incorporation of anions occurs at a later stage of oxidation. The sorption/desorption of solvent molecules also contributes to the mass change observed during the redox transformations of the polymer.     

Electrochemical behavior of thin polycrystalline rhodium layers studied by cyclic voltammetry and quartz crystal microbalance

Electrochemical behavior of thin polycrystalline Rh layers has been studied in 0.5 M H₂SO₄ solution by cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). The properties of surface oxide formed on freshly electrodeposited Rh are different than on electrochemically aged Rh. The analysis of frequency changes in both hydrogen and oxygen regions is presented. It is suggested that hydrogen desorption occurs simultaneously with the adsorption of HSO₄⁻ ions, whose maximum surface coverage reaches ca. 8%. The EQCM results indicate that RhO is the main species formed during Rh surface oxidation. Metal dissolution proceeds during electrode cycling to sufficiently high potentials. The amount of dissolved metal increases with an increase in potential and a decrease in scan rate.     

Electrochemical quartz crystal microbalance study of redox transformations of TCNQ microcrystals in concentrated LiCl solutions

Microcrystals of 7,7,8,8-tetracyanoquinodimethane (TCNQ) immobilized on gold surface have been investigated by combined cyclic voltammetry/chronoamperometry and piezoelectric nanogravimetry at an electrochemical quartz crystal microbalance (EQCM) in dilute and concentrated LiCl solutions. It is proved that TCNQ microcrystals even when TCNQ is reduced to its highly soluble Li⁺TCNQ⁻ salt can be studied in aqueous solutions when the water activity is decreased to a low level. At high electrolyte concentrations the voltammetric and chronoamperometric responses obtained for TCNQ microcrystals show the theoretically predicted pattern characteristic to the solid-solid phase transformation under the control of the nucleation and growth kinetics. The utilization of the idea presented in this work, i.e., using electrolyte of high concentrations (or decreasing the water activity by adding an indifferent component to the liquid phase in high concentration) can open up new vistas in the study of redox transformations of immobilized microcrystals which are soluble in water.     

Temperature dependence of two types of dissolution of platinum in acid media. An electrochemical nanogravimetric study

Smooth and platinized platinum electrodes in contact with sulfuric acid solutions were studied using electrochemical quartz crystal nanobalance (EQCN) technique at different temperatures.Two types of dissolution processes have been observed. A platinum loss was detected during the reduction of platinum oxide, the extent of which depends on the positive potential limit and the scan rate, and to a lesser extent on the temperature. The platinum dissolution during the electroreduction of oxide is related either to the mechanical detachment of Pt atoms which were loosely bounded due to the interfacial place exchange of the oxygen and platinum atoms in the oxide region or to the reduction of Pt(IV) formed at higher positive potentials resulting in soluble Pt²⁺ species. At elevated temperatures two competitive processes take place at high positive potentials: a dissolution of platinum and platinum oxide formation. The presence of dissolved platinum in the solution has been detected by two different methods.These phenomena are of importance regarding the long-term stability of proton exchange fuel cells.     

Study of thiourea adsorption onto polycrystalline gold electrodes

Cyclic voltammetry, differential capacity determinations and chronocoulometry have been employed for quantitative study of thiourea (TU) adsorption at polycrystalline gold/aqueous KClO₄ solution interface. The film pressure and the Gibbs surface excess are determined as functions of potential. The thermodynamic data suggest that the adsorbed TU exhibits distinct surface states which appear when the TU concentration is increased and the potential is more positive.     

Electrochemical quartz crystal microbalance study on carbon oxides adsorption in the presence of electrosorbed hydrogen on Pd alloys with Pt and Rh

CO₂ and CO adsorption on Pd-Pt and Pd-Rh alloys has been studied by cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). Adsorbed CO₂ inhibits partially hydrogen adsorption on Pt and Rh surface atoms but does not block significantly hydrogen absorption into alloy bulk. In the presence of adsorbed CO both hydrogen adsorption and absorption are strongly suppressed. On electrodes covered with adsorbed CO the oxidation of previously absorbed hydrogen is significantly shifted into higher potentials. The EQCM response in CO₂/CO adsorption experiments is affected by both the effects connected with the changes in mass attached to the resonator and the non-mass effects including changes in metal-solution interactions and variation of solution density and viscosity in the vicinity of the electrode. Differences in the EQCM behavior suggest that the products of CO₂ and CO adsorption on the alloys studied are not totally identical.     

Electrochemical quartz crystal impedance study on immobilization of glucose oxidase in a polymer grown from dopamine oxidation at an Au electrode for glucose sensing

Glucose oxidase (GOD) was codeposited into a polymer grown from oxidation of dopamine (DA) at an Au electrode in a neutral phosphate aqueous solution for the first time. The electrochemical quartz crystal impedance analysis (EQCIA) method was used to monitor the GOD-immobilization process. Effects of concentrations of phosphate buffer, DA and GOD were investigated, and the optimal concentrations were found to be 20.0 mM phosphate buffer (pH 7.0), 30.0 mM DA and 5.00 mg ml⁻¹ GOD. A glucose biosensor was thus constructed, and effects of various experimental parameters on the sensor performance, including applied potential, solution pH and electroactive interferents, were examined. At an optimal potential of 0.6 V versus the KCl-saturated calomel electrode (SCE), the current response of the biosensor in the selected phosphate buffer (pH 7.0) was linear with the concentration of glucose from 0.05 to 9 mM, with a lower detection limit of 3 μM (S/N = 3), short response time (within 15 s) and good anti-interferent ability. The Michaelis constant () was estimated to be 9.6 mM. The biosensor exhibited good storage stability, i.e. 96% of its initial response was retained after 7-day storage in the selected phosphate buffer at 4 °C, and even after another 3 weeks the biosensor retained 86% of its initial response. In addition, the enzymatic specific activity and enzymatic relative activity of the GOD immobilized in the polymer from dopamine oxidation (PFDO) were estimated from the EQCIA method to be 1.43 kU g⁻¹ and 3.7%, respectively, which were larger than the relevant values obtained experimentally using poly(o-aminophenol) and poly(N-methylpyrrole) matrices, suggesting that the PFDO is a better matrix to immobilize GOD.     

Interaction of BSA protein with copper evaluated by electrochemical impedance spectroscopy and quartz crystal microbalance

The interaction of bovine serum albumin (BSA) protein with copper in phosphate buffer solution has been studied by a combination of electrochemical impedance spectroscopy (EIS) close to the open circuit potential, with simultaneous monitoring by the electrochemical quartz crystal microbalance (EQCM), in order to throw light on BSA adsorption. Copper films were electroplated onto gold quartz crystals and mounted in the EQCM. Experiments were conducted in the presence and absence of dissolved oxygen and of BSA and the results show the influence of O₂ on the protein/metal interaction and also show specific interactions between BSA and copper. The good reproducibility obtained in these experiments suggests future application to other systems and which should lead to a better understanding of the use of such types of protein as corrosion inhibitors.     

An electrochemical quartz crystal microbalance study into the deposition of manganese dioxide

An electrochemical quartz crystal microbalance (EQCM) has been used to study the effects of electrolyte composition (MnSO₄ and H₂SO₄ concentrations) and anodic current density on the electrodeposition of manganese dioxide. The EQCM, in tandem with the electrode voltage during deposition, has been used to characterize features of the deposition mechanism such as the relative lifetime of the Mn(III) intermediate, the rate of soluble Mn(III) hydrolysis to form MnOOH, and the porosity of the resultant manganese dioxide deposit as a function of crystal nucleation. The connection between the results obtained here and commercial electrodeposition of manganese dioxide were also discussed.     

Investigation of interfacial processes at tetraruthenated zinc porphyrin films using electrochemical surface plasmon resonance and electrochemical quartz crystal microbalance

In the present work we describe the investigation of interfacial and superficial processes on tetraruthenated zinc porphyrin (ZnTRP) films immobilized on gold electrode surface. In situ and real time measurements employing electrochemical surface plasmon resonance (ESPR) and electrochemical quartz crystal microbalance (EQCM) have given new insights into the electrochemical oxidation of ferrocyanide and phenolic compounds (acetaminophen, dopamine, and catechol) on ZnTRP modified electrodes. The decrease of diode like behavior in the presence of such phenolic species in contrast with ferrocyanide was clearly assigned to the inclusion of those species in the porphyrin film, creating new conduction pathways connecting the gold electrode surface with the film/solution interface. In fact, there are evidences that they can intercalate in the film (catechol > dopamine > acetaminophen), whereas ferrocyanide is completely excluded. Accordingly, the molecular size may play a fundamental role in such a process.     

Electrochemical and surface-enhanced Raman spectroscopy studies of 4-phenylpyridine adsorption at the gold/solution interface

The adsorption of 4-phenylpyridine (4-PhPy) on the Au electrode was examined using conventional electrochemical techniques: cyclic voltammetry and impedance measurements and also by surface enhanced Raman spectroscopy (SERS) in a wide range of electrode potentials. Electrochemical results indicate the strong adsorption of 4-Phpy molecules, particularly at the positively charged Au electrode. The wide shoulder of capacity close to the pzc suggests that the composition and/or the structure of 4-Phpy monolayer change with the sign of the surface charge on the electrode. Investigation of integrity of adsorbed layer, however, indicates that adsorbed molecules do not form tight, compact monolayer even in the case of adsorption from saturated solution. SERS spectra provided evidence for gradual, potential-induced reorientation of the molecular plane with respect to the surface, from nearly vertical in the negatively charged electrode, to more flat at the positively charged metal surface.     

In situ FTIR study of 2-chloropyridine adsorbed on Au(111) and Au(110) electrodes

2-chloropyridine (2Clpy) adsorbed on Au(111) and Au(110) electrodes in 0.1 M KClO₄ containing 2 mM 2Clpy has been investigated using in-situ infrared spectroscopy and differential capacity measurements. For both the electrodes, an in-plane ring vibration due to N-bonded 2Clpy was observed, which was accompanied by a loss in the in-plane ring vibrations due to dissolved 2Clpy. However, the integrated band intensity ratios between the adsorbed 2Clpy and the loss of dissolved 2Clpy for both electrodes are quite different in all potentials measured. The relative band intensity of the N-bonded 2Clpy for Au(110) is much stronger than that for the Au(111). This indicates that for the Au(111) the adsorbed 2Clpy is mainly flat type or the tilt angle of the N-bonded 2Clpy is large. It can be explained by the configuration of adsorbed 2Clpy on the electrode surface. For Au(111) terrace, N-bonded configuration is obstructed by the presence of Cl atom. There is no obstruction for the Au(110) step if the N-bonded 2Clpy is adsorbed on the overtop layer.     

Arsenic species interactions with a porous carbon electrode as determined with an electrochemical quartz crystal microbalance

The interactions of arsenic species with platinum and porous carbon electrodes were investigated with an electrochemical quartz crystal microbalance (EQCM) and cyclic voltammetry in alkaline solutions. It is shown that the redox reactions in arsenic-containing solutions, due to arsenic reduction/deposition, oxidation/desorption, and electrocatalyzed oxidation by Pt can be readily distinguished with the EQCM. This approach was used to show that the arsenic redox reactions on the carbon electrode are mechanistically similar to that on the bare Pt electrode. This could not be concluded with just classical cyclic voltammetry alone due to the obfuscation of the faradaic features by the large capacitative effects of the carbon double layer.For the porous carbon electrode, a continual mass loss was always observed during potential cycling, with or without arsenic in the solution. This was attributed to electrogasification of the carbon. The apparent mass loss per cycle was observed to decrease with increasing arsenic concentration due to a net mass increase in adsorbed arsenic per cycle that increased with arsenic concentration, offsetting the carbon mass loss. Additional carbon adsorption sites involved in arsenic species interactions are created during electrogasification, thereby augmenting the net uptake of arsenic per cycle.It is demonstrated that EQCM, and in particular the information given by the behavior of the time derivative of the mass vs. potential, or massogram, is very useful for distinguishing arsenic species interactions with carbon electrodes. It may also prove to be effective for investigating redox/adsorption/desorption behavior of other species in solution with carbon materials as well.     

石英晶体谐振器用高导电率导电胶粘剂的研制

简要介绍了一种高导电率导电胶的研制方法,论述了导电促进剂对性能的影响。实验结果证明,此国产导电胶性能良好,完全可以替代进口导电胶应用于石英晶体谐振器生产中。     

高聚物湿度传感器的研究

本文介绍采用辐射引发聚合的方法制备高聚物/晶振型湿度传感器。通过对高聚物膜的感湿性能测试与评价,确定聚合物膜中各单体组分含量,并优化辐射聚合工艺。该高聚物/晶振型湿度传感器的技术特点是:湿度测量范围宽10％～100％RH;湿滞回差小,测量误差小于±2％RH。尤其适于在易燃易爆环境下应用。     

Application of the electrochemical quartz crystal microbalance technique to copper sonoelectrochemistry: Part 1. Sulfate-based electrolytes

The applicability of the electrochemical quartz crystal microbalance technique in an ultrasonic field created by an ultrasound probe is demonstrated for the electrodeposition of copper. Cyclic voltammetry and potentiostatic depositions in acidic sulfate-based copper electrolytes were performed at different ultrasonic intensities. The electrochemical quartz crystal microbalance was operated in ultrasonic fields with intensities up to 30 W cm⁻². For cyclic voltammetry, potential resolved and averaged (apparent) current efficiencies were calculated from mass and charge data in function of the amplitude of the ultrasonic horn. Ultrasound slightly affected the current efficiencies during copper deposition in cyclic voltammetry, but did not change the efficiencies during dissolution. During potentiostatic depositions the current efficiency increased from 84% to almost 100% upon application of ultrasound. Morphology of deposits prepared by potentiostatic depositions was analyzed by scanning electron microscopy, and found to be different at high ultrasonic intensities.     

A voltammetric and nanogravimetric study of Te underpotential deposition on Pt in perchloric acid medium

This work describes the study of Te underpotential deposition on Pt in acid media using cyclic voltammetry, rotating ring-disc electrode and electrochemical quartz crystal microbalance techniques. The voltammetric results indicate the presence of two dissolution peaks in the positive scan with a total charge density of 420 μC cm⁻². These phenomena are attributed to the deposition of one Te monolayer with the occupancy of two active Pt sites by each ad-atom. This is confirmed by rotating ring-disc electrode results. The electrochemical quartz crystal microbalance (EQCM) experiments yielded the small mass variation of −32 ng cm⁻² (while the theoretical one is −140.4 ng cm⁻² for a complete Te monolayer). This low value can be attributed to the simultaneous adsorption of water, perchlorate anions and the formation of platinum oxide.     

利用石英晶体微量天平测定紫杉醇在二氧化碳中的溶解度

A quartz crystal microbalance (QCM) is used to determine the phase equilibrium of paclitaxel-carbon dioxide system in the pressure range of 0-11 MPa and at temperatures of 35 °C,40 °C and 45 °C.The experimental results indicated that gaseous CO2 could be absorbed poorly into paclitaxel.The swelling of paclitaxel film in CO2 was observed before paclitaxel dissolved into supercritical carbon dioxide (ScCO2) with the increase of pressure.It was found that ScCO2 was not a good solvent for paclitaxel.The mole fraction of paclitaxel in ScCO2 was in the range of (4.5×10-9)-(7.8×10-9) under all our experimental conditions.Therefore,a much higher pressure than the CO2 supercritical point and/or a cosolvent must be used in any processes wherever paclitaxel dissolution in ScCO2 is required.