A study of adsorption behavior of human serum albumin and ovalbumin on hydroxyapatite/chitosan composite

In situ adsorption of human serum albumin (HSA) and ovalbumin (OVA) was real-time monitored by piezoelectric quartz crystal impedance (PQCI) technique to fully understand the initial cellular response on hydroxyapatite/chitosan (HAP/CS) composite. The PQCI parameters, such as resonant frequency (f), static capacitance (C_s), and motional resistance (R_m) were measured for investigating the kinetic adsorption behaviors of both proteins. The change in frequency shifts (Δf) depends on the amount of the adsorbed protein, and the change in motional resistance (ΔR_m) results from the microporosity variation of HAP/CS coating. The results show that the amount of the absorbed HSA is much greater than that of OVA on HAP/CS coating because of the unique construction of HSA as well as a flexible protein. Furthermore, Δf and ΔR_m data were fitted according to the kinetic exponential decay equations. It can be seen that there is only one adsorption process for OVA, but the absorption process for HSA is followed by a rearrangement process, and the former process is faster than the rearrangement process. Subsequently, the composite binding with proteins were demonstrated by the Fourier transform infrared (FTIR), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).     

In situ monitoring of gold-surface adsorption and acidic denaturation of human serum albumin by an isolation-capacitance-adopted electrochemical quartz crystal impedance system

Combined measurements of piezoelectric quartz crystal impedance (PQCI) and electrochemical impedance spectrum (EIS) using a suitable isolation capacitance is reported for the first time to monitor in situ adsorption and acidic denaturation of human serum albumin (HSA) on gold electrodes in Britton-Robinson (B-R) buffers. This method provides simultaneously mutual-interference-free and accurate parameters of EIS and PQCI. Effects of surface thiol-modification, electrode-potential and solution pH on HSA adsorption were examined and discussed. Comparative experiments of HSA adsorption in a B-R buffer of pH 6.42 on bare, cysteine- and 1-dodecanethiol-modified gold electrodes revealed that HSA adsorption is more significant on a hydrophobic (1-dodecanethiol-modified) surface. Insignificant electrode-potential effect implied minor electrostatic effects on HSA adsorption. The adsorption amount of HSA at pH 3.28 was found to be notably greater than those at pH 4.84 and 6.42. To characterize HSA adsorption, electrode standard rate constants (k_s) of the Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ couple were measured before and after HSA adsorption. The k_s-pH curves on an HSA-modified Au electrode revealed that k_s increased abruptly with the decrease of solution pH below pH ∼4. Moreover, pH-dependent responses of the resonant frequency, the motional resistance, the double-layer capacitance, the capacitance of adsorbed HSA layer and the peak absorbance of HSA solutions at 278 nm all exhibited an inflexion change at pH ∼4, and these findings have been explained on the basis of acidic denaturation of HSA and electrical charges carried by HSA molecules.     

Gravimetric monitoring of adsorption behavior of tetrakis(methylpyrdiniumyl)porphyrin onto quartz crystal surface using an electrode-separated piezoelectric sensor

The adsorption behavior of 5,10,15,20-tetrakis (4-N-methylpyridiniumyl)-porphyrin (H₂TMPyP) from aqueous solutions onto a quartz crystal interface was investigated in situ using an electrode-separated piezoelectric sensor (ESPS). With H₂TMPyP adsorbed onto quartz crystal surface of the ESPS, its oscillating frequency decreases linearly with increasing adsorption amount. The adsorption densities obtained in the ESPS method were greater than those determined in a solution depletion method. The influence of surface roughness of quartz crystal and bulk solution properties on the measurement of adsorption density in the ESPS method was discussed.     

Electrodeposited sol-gel-imprinted sensing film for cytidine recognition on Au-electrode surface

A novel thin molecularly imprinted sol-gel film with specific recognition for cytidine was electrodeposited on the surface of piezoelectric quartz crystal (PQC) Au-electrode. In this method, a sufficiently negative potential was applied to the electrode surface to generate hydroxyl ions, which play the role of the catalyst for the hydrolysis and condensation of 3-(aminopropyl)trimethoxysilane (APTMS). The process of the preparation of the imprinted sol-gel film was investigated in detail by using the piezoelectric quartz crystal impedance (PQCI) technique and cyclic voltammetry. The thickness of the imprinted film was controlled easily by adjusting the applied potential and the deposited time. The binding capacity and the selectivity of the electrodeposited imprinted sol-gel film were also studied in detail by using PQCI, electrochemically impedance technique and capacitance technique. The electrodeposited imprinted sol-gel film exhibited high selectivity toward cytidine in comparison to interfering substances. The dissociation constant (K_d) in the nanomolar range indicated a strong imprinted interaction existing between the electrodeposited sol-gel-imprinted film and the template cytidine.     

溶菌酶在裸金电极和疏基乙酸或正十二疏烷基醇修饰电极上的吸附

电化学石英晶体阻抗系统;疏基乙酸;溶菌酶在裸金电极和疏基乙酸或正十二疏烷基醇修饰电极上的吸附     

Adsorption studies of dodecylamine at the quartz interface using an electrode-separated piezoelectric sensor

The adsorption process of dodecylammonium chloride (DAC) from aqueous solutions onto a quartz crystal interface was investigated in situ using an electrode-separated piezoelectric sensor (ESPS). Increasing amounts of DAC adsorbed onto a quartz crystal surface resulted in linearly decreasing oscillating frequencies of the ESPS. The adsorption density can be monitored by the frequency decrease. The adsorption density obtained by calculation using the Sauerbrey equation in the ESPS method is greater than that in solution depletion method. A calibration coefficient is added into the Sauerbrey equation to correct the influence of surface roughness of the quartz crystal on the adsorption density. The influence of solution properties on the adsorption density measurement was discussed. A dependence of the adsorption density on pH was reported. Received: 17 April 1997 / Revised: 1 December 1997 / Accepted: 7 December 1997     

Adsorption studies of dodecylamine at the quartz interface using an electrode-separated piezoelectric sensor

The adsorption process of dodecylammonium chloride (DAC) from aqueous solutions onto a quartz crystal interface was investigated in situ using an electrode-separated piezoelectric sensor (ESPS). Increasing amounts of DAC adsorbed onto a quartz crystal surface resulted in linearly decreasing oscillating frequencies of the ESPS. The adsorption density can be monitored by the frequency decrease. The adsorption density obtained by calculation using the Sauerbrey equation in the ESPS method is greater than that in solution depletion method. A calibration coefficient is added into the Sauerbrey equation to correct the influence of surface roughness of the quartz crystal on the adsorption density. The influence of solution properties on the adsorption density measurement was discussed. A dependence of the adsorption density on pH was reported. Received: 17 April 1997 / Revised: 1 December 1997 / Accepted: 7 December 1997     

A novel dual-impedance-analysis EQCM system--investigation of bovine serum albumin adsorption on gold and platinum electrode surfaces

Both quartz crystal micro-balance (QCM) impedance and electrochemical impedance spectroscopy (EIS) methods are widely used in interface studies. This paper presents details about a new strategy for simultaneous, mutual-interference-free and accurate measurements of QCM impedance and EI, through connecting a suitable capacitance in series with the piezoelectric quartz crystal (PQC) between QCM impedance and EIS measurement instruments. Combined and individual measurements of QCM impedance and EIS during silver deposition gave results comparable with each other, demonstrating the reliability of the proposed method. Bovine serum albumin (BSA) adsorption on gold and platinum electrodes in Britton-Robinson (B-R) buffers was investigated, and the Fe(CN)6(3-)/Fe(CN)6(4-) couple was used as an electrochemical probe to characterize BSA adsorption. While the reversibility of Fe(CN)6(3-)/Fe(CN)6(4-) couple on bare Au and Pt electrodes changed very slightly with decreasing solution pH from pH approximately 7 to pH approximately 2, the standard rate constant (ks) of this couple increased abruptly with solution pH below pH approximately 4.5 at a BSA-modified Au electrode, but decreased with solution pH at a BSA-modified Pt electrode. By analyzing the QCM impedance data with a modified BVD equivalent circuit and the EI data with a modified Randle's equivalent circuit, inflexion changes at pH approximately 4.5 were all found at pH-dependent responses of the resonant frequency, the double-layer capacitance, the capacitance of the adsorbed BSA layer, the peak-absorbance values of BSA solutions at 277.5 and 224.5 nm, and so on. It was also found that a BSA adsorption layer can effectively inhibit gold corrosion during ferrocyanide oxidation in a ferrocyanide-containing BR solution. Some preliminary explanations of these findings have been given. The proposed method is highly recommended for wider applications in surface science.     

Adsorption of metal ions from solution onto a piezoelectric quartz crystal

Many metal ions are spontaneously adsorbed onto a piezoelectric quartz crystal and change the oscillation frequency. The pH ranges in which the metal ions adsorbed were just below that of precipitate formation as the ‘hydroxides’; frequency changes caused by adsorption were not observed in these pH ranges where the ‘hydroxides’ formed. Cationic organic reagents, such as crystal violet and methylene blue, were also adsorbed on the piezoelectric quartz crystal but non-ionic and anionic organic compounds were not. These results showed that the crystal was negatively charged on the surface.     

Adsorption monitoring of phospho-l-serine on hydroxyapatite

The adsorption of the aminoacid phospho-l-serine (PLS) on the surface of hydroxyapatite {Ca₅(PO₄)₃OH, HAP}, was investigated using streaming potential measurements. Solutions saturated with respect to HAP, containing different concentrations of PLS, were brought in contact under carefully controlled flow conditions through plugs made of well dispersed HAP powder. The measurement of PLS adsorption during the equilibration of the solute with the HAP substrate, showed a plateau regime corresponding, according to geometrical considerations, to monolayer surface coverage. The PLS uptake measurements on HAP suggested that it is possible to monitor in situ adsorption during the monolayer surface coverage measuring the streaming potential of HAP. Analysis of the surface potential measurements suggested that during the monolayer surface coverage step, the negatively charged (HL^2?) PLS species were adsorbed. The adsorbed HL^2? was located at the inner Helmholtz plane of the electrical double layer, forming surface complexes with the positively charged ≡CaOH ₂ ⁺ sites on the surface of HAP. The rate constants of adsorption and desorption were calculated from the kinetics of adsorption of PLS on HAP.     

Preparation and Application of Fullerene C60‐Polymers in Piezoelectric Quartz Crystal Sensors for Hemoglobin and Olefins

The C60—polycinnamaldehyde (C₆₀—PCA) and C60—polyphenylacetylene (C60—PPA) polymers were synthesized by the Friedel—Craft reaction and applied as piezoelectric (PZ) quartz crystal coating materials. A C60—polycinnamaldehyde (PCA) coated piezoelectric quartz crystal liquid sensor with a homemade computer interface was prepared and applied as a PZ hemoglobin sensor. The adsorption of hemoglobin onto the C60—PCA coated crystal resulted in a decreased oscillating frequency. The variations in crystal frequency were converted to voltage with a frequency to voltage converter, followed by amplification with OPA and data acquisition with an analog to digital converter. The PZ hemoglobin sensor exhibited good sensitivity of 6530 Hz/(mg/mL) with a detection limit at the ppm level for hemoglobin. Further, a C60—polyphenylacetylene (C60—PPA) coated piezoelectric quartz crystal gas sensor with an Intell‐8255 data processing system for various olefin vapors was also made. The aromatic hydrocarbons such as toluene seem to have greater adsorption onto C60—PPA membrane than alkynes, alkenes, and alkanes. The adsorption of polycyclic aromatic hydrocarbons (PAHs) onto the C60—PPA membrane was also examined. The C₆₀—PPA coated PZ crystal gas sensor showed much better sensitivity for PAHs than for other olefins such as toluene, 1‐hexyne and 1‐hexene, and a much larger frequency shift for naphthalene than other PAHs was also found.     

Piezoelectric quartz crystal impedance and electrochemical impedance study of HSA-diazepam interaction by nanogold-structured sensor

Human serum albumin (HSA) was immobilized on the surface of colloidal Au and exposed to diazepam. Colloidal Au were at first self-assembled on the gold electrode through the thiol groups of a 1,6-hexanedithiol monolayer. The real-time course of the resonant frequency and equivalent circuit parameters of the sensor during the protein-diazepam binding was determined for the first time by piezoelectric quartz crystal impedance (PQCI). On the basis of the multidimensional information provided by the PQCI analysis, it was concluded that the decrement of the observed frequency was mainly ascribable to the mass loading on the sensor surface. Compared with a bare gold electrode, the gold electrode self-assembled from nanogold colloids exhibits maintained biocompatibility, increased capacity, and more bioactivity. Cyclic voltammetry and electrochemical impedance techniques were used to investigate the immobilization of HSA and the interaction between HSA and diazepam. Results testified that gold colloid could play the role of an efficient electron-conducting tunnel and have a very high ratio of surface to volume. Additionally, the kinetics of the binding process was investigated. The estimated binding constant (K) and the number of binding site (n) on one HSA molecule were 1.66 x 10(6) mol l(-1) and 1.28, respectively.     

Interaction between low molecular weight organic acids and hydroxyapatite with different degrees of crystallinity

In this study, two types of hydroxyapatite (HAP) with different degrees of crystallinity were prepared by a sol-gel method and a chemical precipitation method. Influences of crystallinity on the adsorption and dissolution properties of HAP, and the release of phosphorus (total phosphorus) during the adsorption of organic acid were investigated. Results showed that crystallinity had a great effect on the adsorption capacity and dissolution properties of HAP, as well as the adsorption mechanisms of organic acids on HAP surfaces. The poorly crystallized (the degree of crystallinity X_c = 0.23) HAP adsorbed greater amounts of oxalic, citric, or malic acid than the well crystallized (X_c = 0.86) HAP, and the former could release more phosphorus in the presence of organic acids. The adsorption capacity of oxalic acid was much higher than citric and malic acids on both the well and the poorly crystallized HAP, which was due to the strong coordination of oxalic acid with calcium on HAP surface, and that physical adsorption was more inclined to dominate the adsorption of malic or citric acid on the well crystallized HAP. These findings might be of importance in understanding the effects of crystallinity and organic acid binding on the dissolution of calcium phosphates and the adsorption characteristics of HAP.     

Electrochemical piezoelectric quartz crystal impedance study on the interaction between concanavalin A and glycogen at Au electrodes

The carbohydrate research has emerged as a "new frontier" in chemical/biological field. The binding of lectin with carbohydrate is one of the important courses of life activities. The report studies concanavalin A (Con A)-glycogen interaction on gold electrode surfaces by electrochemical piezoelectric quartz crystal impedance (EPQCI) method. The piezoelectric quartz crystal (PQC) parameters, resonant frequency shift (Deltaf(0)) and the motional resistance change (DeltaR(1)), and the electrochemical impedance (EI) parameters, electrolyte resistance change (DeltaR(s)) and the double layer capacitance change (DeltaC(s)), were measured and discussed simultaneously. Two methods were adopted for measuring the Con A-glycogen association. Based on EPQCI measurement during Con A reaction with glycogen adsorbed on Au electrode, association constant K(a) and the amount of the binding sites s calculated are 1.48 x 10(6) M(-1) and 4.09, respectively. Based on single PQC measurement of glycogen reaction with Con A assembled on Au electrode, K(a) was estimated to be 1.26 x 10(6) M(-1).     

Enhanced adsorption of atrazine from aqueous solution by molecularly imprinted TiO2 film

TiO₂ film imprinted by atrazine molecule at the surface of quartz crystal was prepared using molecular imprinting and surface sol-gel process. The molecularly imprinted TiO₂ film was characterized by scanning electron microscopy and cyclic voltammetry, and the atrazine adsorption was investigated by quartz crystal microbalance (QCM) technique. In comparison with non-imprinted TiO₂ film, the molecularly imprinted TiO₂ film exhibits high selectivity for atrazine, better reversibility and a much higher adsorption capacity for the target molecule, the adsorption equilibrium constant estimated from the in situ frequency measurement is about 6.7 × 10⁴ M⁻¹, which is thirteen times higher than that obtained on non-imprinted TiO₂ film.     

Impedance analysis of an electrode-separated piezoelectric sensor as a surface monitoring technique for surfactant adsorption on quartz surface

This paper describes the measurement of the kinetics of adsorption of sodium dodecyl sulfate (SDS), an anionic surfactant, onto a quartz surface with a pre-adsorbed layer of Ca2+ as an ion bridge, using an electrode-separated piezoelectric sensor (ESPS). An impedance analysis method was employed to characterize the responses of the ESPS. The impedance and frequency parameters of the ESPS were examined as functions of the conductivity, permittivity, viscosity and density of the liquid. The adsorption process of SDS onto the quartz surface resulted in an increase in both the mass and energy dissipation of the oscillating quartz crystal. The adsorption densities could be estimated by the ESPS method after taking into consideration the effects of surface viscosity and roughness. The adsorption and desorption rate constants of SDS onto the quartz surface were calculated as ka = (88.1 +/- 0.26) mol(-1) L s(-1) and kd = (4.92 +/- 0.53) x 10(-3) s(-1), respectively, based on the Langmuir model. ESPS was shown to be a powerful means of examining anionic surfactant adsorption to the solid/liquid interface.     

Influence of Gemini Surfactant with Modified TiO2 Nanoparticles on the Interfacial Tension of Oil/Water

The research on the impacts of modified TiO₂ nanoparticles (NPs) on interfacial tension (IFT) is in its infancy. Our work focuses on the IFT of the modified TiO₂ and Gemini surfactant N,N,N′,N′-tetramethyl-N,N′-dimyristyl-1,2-ethane diammonium dichlone (YND1233) complex solutions for reservoir stimulation purposes. The factors of YND1233, modified TiO₂ NPs, temperature, aging stability, adsorption loss, and mineralized degree were explored with the comparison of unmodified TiO₂ NPs and YND1233 as contrast samples. The results indicate that the dynamic IFTs decrease and then increase with the concentrations of YND1233 and modified TiO₂ NPs, and the minimum IFT appears at 0.200 and 0.010 wt%, respectively. YND1233/modified TiO₂ complex solutions show lower and more stable IFTs, better temperature resistance, longer aging time, and lower adsorption on the surface of quartz sand. The modified TiO₂ NPs and YND1233 in the YND1233/modified TiO₂ complex solution can be adsorbed to the interface and decrease the IFTs through synergistic effect. A mixed diffusion-kinetic mechanism is provided for the adsorption and interactions with Ca²⁺/Mg²⁺ involved in YND1233/modified TiO₂ complex solution.     

Real-time monitoring of formaldehyde-induced DNA-lysozyme cross-linking with piezoelectric quartz crystal impedance analysis

A novel method for monitoring, in real time, the formaldehyde (FA)-induced DNA-protein cross-linking process with the piezoelectric quartz crystal impedance (PQCI) technique is proposed. The method was used to monitor FA-induced DNA-lysozyme cross-link formation. Lysozyme was directly immobilized on the silver electrode surface of a piezoelectric quartz crystal by adsorption. The lysozyme-coated piezoelectric sensor was in contact with FA and DNA solutions. The time courses of the resonant frequency and equivalent circuit parameters of the sensor during the cross-linking were simultaneously obtained and are discussed in detail. On the basis of the feature of the multi-dimensional information provided by the PQCI technique, it was concluded that the observed frequency decrease could be mainly ascribed to the mass increase resulting from the cross-linking. According to the frequency decrease with time, the kinetics of the cross-linking process were quantitatively studied. A piezoelectric response model for the cross-linking was theoretically derived. Fitting the experimental data to the model, the kinetic parameters, such as the binding and dissociation rate constants (k(1) and k(-1)) and the cross-linking equilibrium constant (Ka), were determined. At 37 degrees C, the k(1), k(-1) and Ka values obtained were 7.0 (+/-0.1) x 10(-5) (microg ml(-1))(-1) s(-1), 6.6 (+/-0.1) x 10(-3) s(-1) and 1.06 (+/-0.02) x 10(-2) (microg ml(-1))(-1), respectively.     

Mechanism and kinetics of uric acid adsorption on nanosized hydroxyapatite coating

Uric acid (UA) produced from purine metabolism is rather harmful to human health when its concentration is high. To better understand the application of hydroxyapatite (HAP) as an adsorbent for UA removal, quartz crystal microbalance (QCM) technique was employed to in situ investigate the adsorption behavior of UA on nanosized HAP coatings. This work was mainly focused on the mechanism and kinetics of UA adsorption. The obtained results showed that nanosized HAP coatings produced physical adsorption for UA, and the driving force of UA adsorption on HAP coatings was electrostatic interaction. The adsorption kinetic parameter estimated from the in situ frequency measurement was about 3.08?×?10⁶?L/mol. The obtained information suggests that QCM measurement provides a useful method for monitoring the interaction between HAP and UA.     

Effects of Dye‐Adsorption Solvent on the Performances of the Dye‐Sensitized Solar Cells Based on Black Dye

The effects of the dye‐adsorption solvent on the performances of the dye‐sensitized solar cells (DSSCs) based on black dye have been investigated. The highest conversion efficiency (10.6 %) was obtained in the cases for which 1‐PrOH and the mixed solvent of EtOH and tBuOH (3:1 v/v) were employed as dye‐adsorption solvents. The optimized value for the dielectric constant of the dye‐adsorption solvent was found to be around 20. The DSSCs that used MeOH as a dye‐adsorption solvent showed inferior solar‐cell performance relative to the DSSCs that used EtOH, 1‐PrOH, 2‐PrOH, and 1‐BuOH. Photo‐ and electrochemical measurements of black dye both in solution and adsorbed onto the TiO₂ surface revealed that black dye aggregates at the TiO₂ surface during the adsorption process in the case for MeOH. Both the shorter electron lifetime in the TiO₂ photoelectrode and the greater resistance in the TiO₂–dye–elecrolyte interface, attributed to the dye aggregation at the TiO₂ surface, cause the decrease in the solar‐cell performance of the DSSC that used MeOH as a dye adsorption solvent.