Precipitation of different calcite crystal morphologies in the presence of sodium stearate

The influence of sodium stearate (NaSt) on the precipitation of calcium carbonate during the semicontinuous process of slaked lime carbonation was studied in the systems in which process parameters, like concentration of total dissolved calcium, temperature, CO(2) flow rate and initial addition rate of slaked lime, were controlled. It was found that calcite was the only calcium carbonate polymorph that appeared under the investigated experimental conditions, while FT-IR spectroscopy and thermogravimetric analysis of samples confirmed the presence of stearate on the surface of precipitated calcium carbonate (PCC). Specific surface area of PCC increased with increasing stearate content: the highest value, s = 52.8 m(2) g(-1), was obtained at t = 20 degrees C, c(tot) = 17.0 mmol dm(-3) and the stearate content of m(NaSt)/m(CaO) = 0.03. It was also found that hydrophobic calcite crystals in the form of rhombohedral and scalenohedral morphology can be produced at m(NaSt)/m(CaO) > 0.01. The exception is the case of nanosized PCC production, when much higher concentration of NaSt is needed, m(NaSt)/m(CaO) = 0.22. Minimal amount of stearate necessary to build up the monolayer and corresponding cross sectional area of one stearate molecule were estimated for the obtained calcite morphologies.     

Pyrene fluorescence at air/sodium dodecyl sulfate solution interface

The dependence of pyrene fluorescence spectra on the concentration of sodium dodecyl sulfate (SDS) was observed, where the solution was prepared from water saturated with pyrene. The values of the I(1)/I(3) ratio from the bulk solution and from the upper meniscus region in an optical cell were similar but decreased rapidly around the critical micelle concentration (cmc) of SDS, indicating that pyrene molecules preferred to be solubilized in the micelles having a lower dielectric constant. The fluorescence intensity of the excimer indicated the concentration of pyrene molecules at the air/solution interface or the surface activity of pyrene molecules. In addition, the intensity from the meniscus region is much larger than that from the bulk at the concentrations below the cmc, whereas there was no difference in the intensity between the bulk and the meniscus above 8 mmol dm(-3) of SDS. The analysis of the fluorescence intensity from the excimer strongly suggests the presence of molecular aggregates that are favorable to the pyrene molecules just like the micelles in the bulk, making them less movable.     

Solubilization study for aggregates of sodium dodecyl sulfate and cationic polymer of high charge density

Interaction of sodium dodecyl sulfate (SDS) with a cationic polymer (polydiallyldimethylammonium chloride, PDADMAC) was investigated. The surface tension of SDS/PDADMAC solution ([PDADMAC]=100 ppm) decreased from 72 to ca. 40 mN m(-1) with increasing SDS concentration at 298.2 K, where the SDS concentration, 0.6 mmol dm(-3), at 40 mN m(-1) was less than cmc/10 of SDS. From the relatively high value of I1/I3, ca. 1.5, in the pyrene fluorescence spectrum, which is larger than the value in SDS micelles, the aggregation number is suggested to be lower than that of SDS micelles. The maximum additive concentration for n-alkylbenzenes as solubilizate increased with the increase in SDS concentration and with decreasing alkyl chain length of the solubilizates. The Gibbs energy changes for their solubilization from the phase separation model were almost the same as those from the mass action model for longer chain solubilizates, due to their smaller solubilized amounts in the micelles. The Gibbs energy change for the solubilization decreased with increasing alkyl chain length of the solubilizates. The Gibbs energy decrease per CH2 group (deltaG(CH2)0) was larger in magnitude than for micelles of single-surfactant systems, which was substantiated by the absorption spectrum change of the solubilizates.     

Polymerized rodlike nanoparticles with controlled surface charge density

Stable rodlike nanoparticles with highly controlled surface charge density have been developed by the free radical polymerization of the mixture of polymerizable cationic surfactant, cetyltrimethylammonium 4-vinylbenzoate (CTVB), and hydrotropic salt sodium 4-styrenesulfonate (NaSS) in aqueous solution. The surface charge of the polymerized CTVB/NaSS rodlike nanoparticles was controlled by varying the NaSS concentration during the polymerization process, and the charge variation was interpreted in terms of the overcharging effect in colloidal systems. The SANS measurements show that the diameter of the polymerized CTVB/NaSS rodlike nanoparticles is constant at 4 nm and the particle length ranges from 24 to 85 nm, depending on the NaSS concentration. The polymerized particles are longest when the NaSS concentration is 5 mol % which corresponds to the charge inversion or neutral point. The SANS and zeta potential measurements show that the Coulomb interactions between the particles are strongly dependent on the NaSS concentration and the zeta potential of the polymerized CTVB/NaSS nanoparticles changes from positive to negative (+12.8 approximately -44.2 mV) as the concentration of NaSS increases from 0 to 40 mol %. As the NaSS concentration is further increased, the zeta potential is saturated at approximately -50 mV.     

Structure of synthetic calcium hydroxyapatite particles modified with pyrophosphoric acid

Synthetic colloidal calcium hydroxyapatite (Ca(10)(PO(4))(6)(OH)(2): CaHap) was treated with pyrophosphoric acid (H(4)P(2)O(7): PP) in acetone and the materials were characterized by XRD, TEM, FTIR, and N(2) and H(2)O adsorption measurements. XRD patterns and morphology of CaHap particles were essentially not changed by the modification. The additional amount of PO(4) of CaHap was increased with an increase of PP concentration and the Ca/P molar ratio of the particles decreased from 1.62 to 0.81. IR results indicated that the isolated surface POH band developed with increasing the PP concentration up to 6.0 mmol dm(-3) by the reaction of isolated surface POH groups of CaHap and pyrophosphoric acids. Above 10.2 mmol dm(-3), a hydrogen-bonding surface POH band appeared at 2913 cm(-1) and enlarged with increasing the PP concentration, while the isolated surface POH band was weakened. The results of N(2) and H(2)O adsorption measurements revealed that the modified particles aggregated compared to the unmodified ones, which would be due to the formation of hydrogen-bonding surface POH groups among the particles.     

Quartz crystal microbalance with dissipation monitoring and surface plasmon resonance studies of carboxymethyl cellulose adsorption onto regenerated cellulose surfaces

Adsorption of anionic polyelectrolytes, sodium salts of carboxymethyl celluloses (CMCs) with different degrees of substitution (DS = 0.9 and 1.2), from aqueous electrolyte solutions onto regenerated cellulose surfaces was studied using quartz crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance (SPR) experiments. The influence of both calcium chloride (CaCl(2)) and sodium chloride (NaCl) on CMC adsorption was examined. The QCM-D results demonstrated that CaCl(2) (divalent cation) caused significantly greater CMC adsorption onto regenerated cellulose surfaces than NaCl (monovalent cation) at the same ionic strength. The CMC layers adsorbed onto regenerated cellulose surfaces from CaCl(2) solutions exhibited greater stability upon exposure to flowing water than layers adsorbed from NaCl solutions. Both QCM-D and SPR results showed that CMC adsorption onto regenerated cellulose surfaces from CaCl(2) solutions increased with increasing CaCl(2) concentration up to the solubility limit (10 mM). Voigt-based viscoelastic modeling of the QCM-D data indicated that the CMC layers adsorbed onto regenerated cellulose surfaces had shear viscosities of η(f) ≈ 10(-3) N·s·m(-2) and elastic shear moduli of μ(f) ≈ 10(5) N·m(-2). Furthermore, the combination of SPR spectroscopy and QCM-D showed that the CMC layers contained 90-95% water. Adsorption isotherms for CMCs in CaCl(2) solutions were also obtained from QCM-D and were fit by Freundlich isotherms. This study demonstrated that CMC adsorption from CaCl(2) solutions is useful for the modification of cellulose surfaces.     

Physicochemical properties of quaternized poly(amidoamine) dendrimers with four octyl chains

A cationic dendrimer-type tetrameric surfactant (C(8)qbG0) with four octyl chains and four ammonium groups was synthesized by the reaction of poly(amidoamine) dendrimers with generation of zero and glycidyldimethyloctylammonium bromide. The physicochemical properties of C(8)qbG0 and of their mixtures with sodium dodecyl sulfate (SDS) were characterized by investigating surface tension, electrical conductivity, fluorescence of pyrene, and dynamic light-scattering. The critical micelle concentration (cmc) of C(8)qbG0 was 13 mmol dm(-3) at the concentration of one terminal group and the surface tension at the cmc attained 34 mN m(-1). The occupied area of C(8)qbG0 was 1.94 nm(2) molecule(-1), indicating that the tetrameric dendrimers adsorb widely at the air/water interface. The fluorescence intensity ratio of the first-to-third band in the emission spectra of pyrene for C(8)qbG0 decreased from around the cmc obtained by the surface tension measurement. The hydrodynamic radius of C(8)qbG0 determined by dynamic light-scattering was about 1.3 nm. The addition of SDS to the aqueous solutions of C(8)qbG0 enhanced the surface activities; the mixtures exhibited lower cmc, lower surface tension, and higher solubilization of pyrene than SDS alone. It was found that the mixtures of C(8)qbG0 and SDS form large aggregates due to the interactions between their alkyl chains as well as hydrophilic groups.     

Templating CdSe tetrapods at the air/water interface with POPC lipids

ZnS nanoparticles were precipitated in aqueous dispersions of cationic surfactant cetyltrimethylammonium bromide (CTAB). The sphere radii of ZnS nanoparticles calculated by using band-gap energies steeply decreased from 4.5 nm to 2.2 nm within CTAB concentrations of 0.4-1.5 mmol L(-1). Above the concentration of 1.5 mmol L(-1), the radii were stabilized at R=2.0 nm and increased up to R=2.5 nm after 24 h. The hydrodynamic diameters of CTAB-ZnS structures observed by the dynamic light scattering (DLS) method ranged from 130 nm to 23 nm depending on CTAB concentrations of 0.5-1.5 mmol L(-1). The complex structures were observed by transmission electron microscopy (TEM). At the higher CTAB concentrations, ZnS nanoparticles were surrounded by CTA(+) bilayers forming positively charged micelles with the diameter of 10nm. The positive zeta-potentials of the micelles and their agglomerates were from 16 mV to 33 mV. Wurtzite and sphalerite nanoparticles with R=2.0 nm and 2.5 nm covered by CTA(+) were modeled with and without water. Calculated sublimation energies confirmed that a bilayer arrangement of CTA(+) on the ZnS nanoparticles was preferred to a monolayer.     

Electrokinetics at high ionic strength and hypothesis of the double layer with zero surface charge

A growing number of publications in the last two decades have suggested that the structure and other properties of the interfacial water layer can significantly affect the double layer (DL) because of changes in ion solvatation energy. Most interesting is the possibility that a double layer might in fact exist, even when there is no electric surface charge at all, solely because of the difference in cation and anion concentrations within this interfacial water layer. Dukhin, Derjaguin, and Yaroschuk suggested this possibility 20 years ago and developed a phenomenological theory. Recently, Mancui and Ruckenstein created more sophisticated microscopic model. In this article, we present our first experimental result regarding the verification of this "zero surface charge" DL model. The electroacoustic technique allows testing at high ionic strength (up to 2 M). As a first step, we confirm the surprising result of Johnson, Scales, and Healy regarding large zeta potential of alumina (8 +/- 1 mV) in 1 M KCl. As a second step, we suggest using nonionic surfactant Tween 80 for probing and modifying the structure of the interfacial layer at high ionic strength. The application of surfactant at moderate ionic strength (i.e., <0.1 mol/dm3), as might be expected, reduces the zeta potential simply by shifting the slipping plane. However, there is no influence of surfactant on the zeta potential observed at high ionic strength. It turns out that a high concentration of KCl simply eliminates surfactant adsorption. We develop a new technique for characterizing the adsorption of nonionic surfactant using an acoustic attenuation measurement. We hope that these methods in combination with a proper surfactant and electrolyte selection would allow us to gain more detailed information on the interface structure at high ionic strength.     

Preparation and characterization of biosurfactant based on hydrophobically modified alginate

Hydrophobic modified alginate (HM-alginate) was synthesized using a low-energy, environment-friendly process in aqueous solution, with sodium alginate and dodecyl glycidyl ether as starting materials. The HM-alginate was characterized using ¹H NMR, and the reaction efficiency was about 40%. The HM-alginate aggregated in solution; the critical micelle concentration (CMC) was determined using surface tension and dynamic light scattering methods. We observed reasonable agreement between the CMC values obtained by the different techniques, and the CMC was 4.0 × 10^?4 g/mL. The zeta-potential of the HM-alginate in aqueous solution was about ?82 mV, which is higher than ?51 mV of the sodium alginate. Rheology measurements showed that the HM-alginate solution exhibits a Newtonian behavior at all shear rates, whereas the apparent viscosity is very low. The solubility of the liposoluble substance Sudan IV increased significantly with HM-alginate concentration. This result is promising for potential applications of HM-alginate as an ecology-safe material to encapsulate lipophilic substances.     

Zeta potential of anoxygenic phototrophic bacteria and Ca adsorption at the cell surface: possible implications for cell protection from CaCO3 precipitation in alkaline solutions

Electrophoretic mobility measurements and surface adsorption of Ca on living, inactivated, and heat-killed haloalkaliphilic Rhodovulum steppense, A-20s, and halophilic Rhodovulum sp., S-17-65 anoxygenic phototrophic bacteria (APB) cell surfaces were performed to determine the degree to which these bacteria metabolically control their surface potential equilibria. Zeta potential of both species was measured as a function of pH and ionic strength, calcium and bicarbonate concentrations. For both live APB in 0.1M NaCl, the zeta potential is close to zero at pH from 2.5 to 3 and decreases to -30 to -40 mV at pH of 5-8. In alkaline solutions, there is an unusual increase of zeta potential with a maximum value of -10 to -20 mV at a pH of 9-10.5. This increase of zeta potential in alkaline solutions is reduced by the presence of NaHCO(3) (up to 10 mM) and only slightly affected by the addition of equivalent amount of Ca. At the same time, for inactivated (exposure to NaN(3), a metabolic inhibitor) and heat-killed bacteria cells, the zeta potential was found to be stable (-30 to -60 mV, depending upon the ionic strength) between pH 5 and 11 without any increase in alkaline solutions. Adsorption of Ca ions on A-20s cells surface was more significant than that on S-17-65 cells and started at more acidic pHs, consistent with zeta potential measurements in the presence of 0.001-0.01 mol/L CaCl(2). Overall, these results indicate that APB can metabolically control their surface potential to electrostatically attract nutrients at alkaline pH, while rejecting/avoiding Ca ions to prevent CaCO(3) precipitation in the vicinity of cell surface and thus, cell incrustation.     

Amperometric detection with microelectrodes in flow injection analysis: theoretical aspects and application in the determination of nitrite in saliva

The construction of a wall-jet cell with amperometric detection using a set of disc electrodes whose radii ranged from 5 to 750 mum has been proposed. The influence of some experimental parameters like flow rate and electrode radius on hydrodynamic voltammograms recorded for a 0.5 mmol dm(-3) potassium ferrocyanide solution also containing 0.1 mol dm(-3) KCl has been discussed. Some considerations regarding the current signals obtained from flow injection experiments using both a 5- and a 750-mum radius platinum electrode were carried out in order to achieve the lowest limit of detection, a value of 0.03 mumol dm(-3) ferrocyanide being calculated by using the 5-mum radius microelectrode as amperometric detector. The wall-jet cell has been used in the determination of nitrite in saliva by quantifying the triiodide formed in the reaction of the analyte with excess iodide in acidic medium. A 12.5-mum platinum disc microelectrode maintained at +0.2 V vs. Ag/AgCl was used as amperometric detector. Peaks obtained in fiagrams after injection of diluted saliva to the carrier stream containing 0.1 mol dm(-3) sulphuric acid and 20 mmol dm(-3) potassium iodide were compared to an analytical curve obtained in the same conditions (r(2)=0.997) for a nitrite concentration in the range 1-10 mumol dm(-3). The concentration of nitrite in the saliva sample after the appropriate correction for dilution was found to be 2.3 ppm (0.05 mmol dm(-3)), in a good agreement with results obtained by using a standard spectrophotometric procedure (2.5 ppm). The limit of detection of the method was calculated as 0.2 mumol dm(-3), and the reproducibility was checked by measuring the peak current for 19 injections of 10 muM nitrite, the standard deviation being 3.7%.     

Influence of gas flow rate and sodium carboxymethylcellulose on foam properties of fatty alcohol sodium polyoxyethylene ether sulfate solution

Foamability, foam initial liquid volume, and bubble size of fatty alcohol sodium polyoxyethylene ether sulfate (AES) surfactant solution were studied with and without the addition of sodium carboxymethylcellulose (CMC) at different gas flow rates, using a sparging method. The generation time decreased with increasing gas flow rate. At low gas flow rates, the added CMC greatly enhanced the foamability by preventing bubble collapse. The initial liquid volume of the foam first increased rapidly, and then gradually decreased. Increasing the CMC concentration increased the initial liquid volume of the foam. The mean bubble diameter first clearly decreased, then increased slowly with increasing gas flow rate. CMC showed different effects on bubble size at high and low gas flow rates. Adsorption of CMC on AES molecules forms a network structure and improves bubble film stability, which can explain the above results. These findings provide guidelines for generating foam with excellent properties suitable for coal mine dust control by adjusting the gas flow rate and the concentration of the added water-soluble polymer.     

A study of the effect of proteins and endogenous cations on a lipophilic beta-cyclodextrin-based potentiometric lidocaine sensor using discrete solution and flow-injection analysis

2,6 Didodecyl beta cyclodextrin (2,6ddbetaCD) modified ion-selective electrodes (ISEs) were used in discrete solutions and in a flow injection analysis manifold for monitoring the local anaesthetic lidocaine hydrochloride (lignocaine) in the presence of endogenous cations and proteins. Membrane matrices comprised of either high molecular weight poly (vinyl chloride) (PVC) or polyurethane (Tecoflex SG 80) were compared. The behaviour of these electrodes in the presence of bovine serum albumin (BSA), alpha(1) acid glycoprotein (AAG) and human serum (HS) indicate that the Tecoflex-based membrane matrices are preferable to PVC as the drift induced by proteins on baseline lines and peak height reproducibility was considerably reduced in the former. Interference from 'serum' levels of sodium, potassium and calcium (145 mmol dm(-3) Na(+), 1.26 mmol dm(-3) Ca(2+), 4.30 mmol dm(-3) K(+)) was negligible (-Log K(ij)(POT) (overall) >/=4.0). The major organic interferents were molecules of similar size and structure, which caused reduced slope and drift in baseline potentials, at equimolar concentration levels. A reduction in interferent concentration by a factor of 10 negated these effects.     

Binary mixed micelles of chiral sodium undecenyl leucinate and achiral sodium undecenyl sulfate: I. Characterization and application as pseudostationary phases in micellar electrokinetic chromatography

Sodium 10-undecenyl sulfate (SUS), sodium 10-undecenyl leucinate (SUL) and their five different mixed micelles at varied percent mole ratios were prepared. The critical micelle concentration (CMC), C₂₀, γ_CMC, partial specific volume, methylene group selectivity, mobilities and elution window were determined using a variety of analytical techniques. These surfactant systems were then evaluated as novel pseudostationary phases in micellar electrokinetic chromatography (MEKC). As a commonly used pseudostationary phase in MEKC, sodium dodecyl sulfate (SDS) was also evaluated. The CMC values of SUS and SUL were found to be 26 and 16 mM, respectively, whereas the CMC of mixed surfactants was found to be very similar to that of SUL. The C₂₀ values decreased dramatically as the concentration of SUL is increased in the mixed micelle. An increase in SUL content gradually increased the methylene group selectivity making the binary mixed surfactants more hydrophobic. Linear solvation energy relationships (LSERs) and free energy of transfer studies were also applied to predict the selectivity differences between the surfactant systems. The cohesiveness and the hydrogen bond acidic character of the surfactant systems were found to have the most significant influence on selectivity and MEKC retention. The SUS and SDS showed the strongest while SUL showed the weakest hydrogen bond donating capacity. The basicity, interaction with n and π-electrons of the solute and dipolarity/polarizability were the least significant factors in LSER model for the surfactant systems studied. Free energies of transfer of selected functional groups in each surfactant systems were also calculated and found to be in good agreement with the LSER data.     

Nitrite reduction and detection at a carbon paste electrode containing hemoglobin and colloidal gold

A novel renewable reagentless nitrite biosensor based on the direct electron transfer of hemoglobin (Hb) and a new sensing mechanism was proposed by combining the advantageous features of colloidal gold nanoparticle and carbon paste technology. The direct electrochemistry of immobilized Hb displayed a pair of redox peaks with a formal potential of -42 mV (vs. NHE) in 0.2 mol dm(-3) NaAc-HAc buffer (pH 5.5). The immobilized Hb displayed an excellent response to the reduction of NO2(-) with one interfacial charge transfer followed by a chemical reaction (EC) mechanism. Under optimal conditions, the interfacial EC process could be used for the sensitive determination of NO2(-) with a linear range from 0.1 to 9.7 micromol dm(-3) and a detection limit of 0.06 [micro sign]mol dm(-3) at 3sigma. The amperometric determination of high concentrations of NO2(-) based on the irreversible reduction of NO could be performed at pH 4.0 with a linear range from 0.1 to 1.2 mmol dm(-3). The surface of biosensor could be renewed quickly and reproducibly by a simple polish step. The biosensor has been used satisfactorily for nitrite determination in native water samples.     

Light Scattering Study of the Effect of n-Butanol on the Micellar Properties of Undecylammonium Chloride in Aqueous Electrolyte Solutions

Light scattering measurements have been performed on aqueous solutions of undecylammonium chloride in the presence of 0 to 0.2 mol dm(-3) NaCl and 0 to 0.5 mol dm(-3) n-butanol at 25 degrees C. The critical micelle concentration (CMC), aggregation number, and degree of dissociation of the micelles have been determined. The observed decrease of the CMC with the increase of the n-butanol concentration was explained by the effect of the n-butanol on water structure and by the selective solvation of the micelles with n-butanol, which counteract the decrease of the polar character of the solvent caused by n-butanol addition. An observed increase in the degree of dissociation of the micelles and a decrease in the aggregation number following alcohol addition have been explained by considering the effect of this additive on the electrostatic and other interactions involved in free energy of micellization. Our results support the concept of opposing effects between n-butanol and NaCl on the cooperativity in the micellization process of this surfactant, with the n-butanol disfavoring micellar growth. Copyright 2000 Academic Press.     

Binding of sodium dodecyl sulfate to linear and star homopolymers of the nonionic poly(methoxyhexa(ethylene glycol) methacrylate) and the polycation poly(2-(dimethylamino)ethyl methacrylate): electromotive force, isothermal titration calorimetry, surface tension, and small-angle neutron scattering measurements

We investigated the binding of sodium dodecyl sulfate (SDS) to various linear and star polymers of the nonionic methoxyhexa(ethylene glycol) methacrylate (PMHEGMA) and the ionic 2-(dimethylamino)ethyl methacrylate (PDMAEMA), the latter being a polycation at low pH. The dodecyl sulfate ion selective electrode (EMF), isothermal titration calorimetry (ITC), and surface tension (ST) were applied to gain detailed information about interactions. In all cases there is evidence of significant binding of SDS over an extensive SDS concentration range spanning from ca. 10(-6) to 0.1 mol dm(-3). At pH 3, the polymer PDMAEMA is a strong polycation and here the binding is dominated by electrostatic 1:1 charge neutralization with the anionic surfactant. At their natural pH of 8.6, PMHEGMA and PDMAEMA polymers are essentially nonionic and bind SDS in the form of polymer-bound aggregates in the concentration range of ca. 1 x 10(-3) to 3 x 10(-2) mol dm(-3). All the polymers also bind SDS to a lesser extent at concentrations below 1 x 10(-3) mol dm(-3) reaching as low as 10(-7) mol dm(-3). This low concentration binding process involves the polymer and nonassociated SDS monomers. As far as we are aware, this is the first example that such a low concentration noncooperative binding process could be observed in SDS/neutral polymer systems by EMF and ST. We also showed that the nonionic surfactant hexa(ethylene glycol) mono-n-dodecyl ether (C12EO6) and the cationic cetyltrimethylammonium bromide (C16TAB) interact with star PDMAEMA. We believe that the interaction of C12EO6 and CTAB is of similar noncooperative type as the first SDS binding process in the range from ca. 10(-5) to 0.3 x 10(-3) mol dm(-3). At the high concentration binding limit Csat of SDS, the above polymers become fully saturated with bound SDS micelles. We applied small angle neutron scattering (SANS) to determine the structure and aggregation numbers of the star polymer/bound SDS micelles and calculated the stoichiometry of such supramolecular complexes. The SANS data on PDMAEMA star polymers in the presence of C12EO6 showed only a limited monomer binding in contrast to linear PDMAEMA, which showed monomer C12EO6 binding at low concentrations but micellar aggregates at 6 x 10(-3) mol dm(-3).     

Effect of pH on adsolubilization of single and binary organic solutes into a cationic hydrocarbon surfactant adsorbed layer on silica

The adsolubilization behaviors of 2-naphthol, biphenyl, and their binary solutes in the hexadecyltrimethyl ammonium bromide (HTAB) adsorbed layer formed on silica have been studied with solution pH. Two feed concentrations of HTAB are employed: 1.5 and 3.0 mmol dm(-3). At the feed concentration of 1.5 mmol dm(-3) HTAB, most of HTAB are adsorbed on the silica as a monolayer, while a bilayer formation occurs at the feed concentration of 3.0 mmol dm(-3). It is found that the adsolubilized amounts of respective single solutes increase with increasing solution pH except acidic region for biphenyl under a constant feed concentration of 2-naphthol (0.4 mmol dm(-3)) and biphenyl (0.047 mmol dm(-3)). The adsolubilization of binary solutes depends on the feed concentration of HTAB; at the low HTAB feed concentration, competitive adsolubilization between 2-naphthol and biphenyl occurs above pH 4.5, while at the high HTAB feed concentration the adsolubilization of biphenyl is enhanced by the incorporation of 2-naphthol over a whole pH region. These behaviors in the adsolubilization are discussed from the surfactant structure of HTAB adsorbed as well as the admicellar partitioning coefficients.     

Temperature-induced reversible change in the redox response in phenothiazine-labeled poly(ethoxyethyl glycidyl ether) and its application to the thermal control of the catalytic reaction of glucose oxidase

Novel redox-active thermosensitive polymers (phenothiazine-labeled poly(ethoxyethyl glycidyl ether), PT-PEEGE), composed of a polyoxyalkylene backbone, ethoxyethoxymethyl side chains, and an electroactive phenothiazine end group, were prepared by base-catalyzed anionic ring-opening polymerization of ethoxyethyl glycidyl ether monomer in the presence of 10-(2-hydroxyethyl)phenothiazine. Phase separation of a 1.0 mmol dm(-3) (0.33 wt %) PT-PEEGE aqueous solution occurs at 28 degrees C. While the phase separation temperature (Tc) is almost constant in the concentration range above 1.0 mmol dm(-3), it increases at below 1.0 mmol dm(-3). A 10-fold decrease in the oxidation current of PT-PEEGE is observed above Tc and reflects the decrease in the apparent concentration of electroactive PT-PEEGE due to the phase separation. The redox response mainly comes from PT-PEEGE molecules in the dilute phase, resulting from the phase separation, and the half-wave potential and peak separation are independent of the phase separation. This thermally induced change in the redox response is reversible and is applied for the thermal control of the electrocatalytic reaction of glucose oxidase (GOx). The catalytic current in the presence of PT-PEEGE as an electron mediator decreases at temperatures higher than Tc. This originates from the phase separation of PT-PEEGE, and PT-PEEGE molecules which remained to be soluble participate in the electrocatalytic reactions of GOx as mediators.