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Monolayers of n-eicosanephosphonic acid, EPA, were studied using a Langmuir balance and a Brewster angle microscope at different subphase pH values to change the charge of the polar headgroups (Zav) from 0 to -2. Molecular dynamics simulations (MDS) results for |Zav| = 0, 1, and 2 were compared with the experimental ones. EPA monolayers behave as mixtures of mutually miscible species (C20H41-PO3H2, C20H41-PO3H(-), and C20H41-PO3(2-), depending on the subphase pH). The order and compactness of the monolayers decrease when increasing |Zav|, while go from strongly interconnected by phosphonic-phosphonic hydrogen bonds (|Zav| = 0-0.03) through an equilibrium between the total cohesive energy and the electrostatic repulsion between the charged polar groups (0.03 < |Zav| < 1.6) to an entirely ionic monolayer (|Zav| ≈ 2). MDS reveal for |Zav| = 0 that the chains form spiralled nearly rounded structures induced by the hydrogen-bonded network. When |Zav| ≈ 1 fingering domains were identified. When Z ≈ 2, the headgroups are more disordered and distanced, not only in the xy plane but also in the z direction, forming a rough layer and responding to compression with a large plateau in the isotherm. The monolayers collapse behavior is consistent with the structures and domains founds in the different ionization states and their consequent in-plane rigidity: there is a transition from a solid-like response at low pH subphases to a fluid-like response at high pH subphases. The film area in the close-packed state increases relatively slow when the polar headgroups are able to form hydrogen bonds but increases to near twice that this value when |Zav| ≈ 2. Other nanoscopic properties of monolayers were also determined by MDS. The computational results confirm the experimental findings and offer a nanoscopic perspective on the structure and interactions in the phosphonate monolayers.

It has been proposed that disk-like micelles may be precursors to the formation of lamellar liquid crystals. The possibility of obtaining n-decane phosphonic acid (DPA) disk-like micelles in aqueous solution without the addition of a second ionic surfactant led us to study in detail the low-concentration range of this system by both a battery of experimental techniques and molecular dynamics (MD) simulations. The experimental results indicate that premicelles with some capacity to solubilize dyes are formed at 0.05 mM. The critical micelle concentration (cmc) was found to be 0.260 ± 0.023 mM, much lower than that previously reported in the literature. Spherical micelles, which immediately grow, leading to disk-like micelles, are probably formed at this concentration. At 0.454 ± 0.066 mM, disk-like micelles become unstable, giving rise to the formation of an emulsion of lamellar mesophase that dominates the system beyond 0.670 ± 0.045 mM. These experimental results were corroborated by MD simulations which, additionally, allow describing the structure of the obtained micelles at atomic level. The analysis of the MD trajectories revealed the presence of strong intermolecular hydrogen bonds between the surfactant headgroups, producing a compact polar layer with low water content. The formation of such H-bond network could explain the ability of this surfactant to form disk-like micelles at concentrations close to the cmc.

The adsorption and photodegradation of acridine orange (AO) and acriflavine (AF) dyes on two mesoporous titania crystalline phases, anatase and rutile, were experimentally studied. Anatase and rutile were characterized by nitrogen adsorption, electron scanning and transmission microscopy, and X-ray diffraction. The adsorption capacity of rutile was higher than that of anatase, while the reverse is observed for photodegradation of both dyes. The adsorption of AF on both adsorbents was higher than that of AO, which was related with the smaller size of AF molecules compared with those of AO, therefore the access of AF to the adsorption sites is favored., (Copyright © 2012. Published by Elsevier Ltd.)

The aggregation properties of 2-, 3-, and 4-fluorobenzoic acids (2FBA, 3FBA, and 4FBA, respectively) and their salts with hexadecyltrimethylammonium cations (HTA2FB, HTA3FB, and HTA4FB) in water were studied with a battery of techniques. Their activity at the air/solution interface has been also studied. The position of the fluorine atom in the acid affected the solubility, adsorption, and aggregation in the pure acids solutions. The 4FBA is less water soluble, more hydrophobic, and has the lower critical aggregation concentration of the three isomers. The behavior of the HTA2FB compound in aqueous solution is different from that of HTA3FB and HTA4FB. The critical micelle concentration, critical concentration for sphere-to-rod-like micelle transition, and Krafft point of HTA3FB and HTA4FB are lower than those of the other surfactant but their surface activities are higher. The differences between the HTA2FB and the other two surfactants have been explained on the basis of the regular solution theory of mixed micelles and in light of the analysis of the hydration shell of the acids through molecular dynamic simulations. The results of the present work suggest that the different behaviors are due to a combination of different dehydration tendencies and the steric possibility of inclusion of the counterions in the micelle palisade layer. The formation of rod-like micelles by HTA2FB, while the tetradecyltrimethylammonium 2-fluorobenzoate only forms spherical aggregates, is explained on the basis of the packing parameter. The mentioned factors are complementary to others presented in literature. These conditions may be used in the rational design of micelles by means of molecular dynamics simulations, reducing the trial-and-error approach used to date., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Mesoporous silica materials were synthesized in alkaline and acidic media, using cetyltrimethylammonium tosylate (CTAT), Pluronic triblock copolymers F127 and F68, and mixtures of CTAT with each copolymer in order to investigate the effects of pH, surfactant concentration, and CTAT/triblock copolymer molar ratios on the morphology and texture of the synthesized materials. The results show that the kind of mesoporous materials and their pore size can be tuned by changing not only the pH but also the proportion of components and the nature of the copolymer. In alkaline synthesis, microscopic bicontinuous materials are obtained, which are composed by nanoscopic plate-like particles having slit-shaped pores. In acidic synthesis, on the contrary, monolithic silicas are obtained. These materials are also composed by nanoscopic plate-like particles having slit-shaped pores, although in some cases, the microscopic structures are formed by fused spherical particles. The inclusion of the triblock copolymer in the template composition causes a transformation from a bimodal to a monomodal pore size distribution, leading to small and nearly round pores which are probably formed by copolymer or copolymer-CTAT mixed micelles. The differences between the systems synthesized by CTAT-Pluronic F127 and CTAT-Pluronic F68 are explained on the basis of the different interactions between each copolymer and CTAT., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Ascorbyl palmitate (Asc16) in polyethyleneglycol 400 (PEG 400)-water mixtures at weight fractions (w/w) between 0.05 and 1.0 were studied by differential scanning calorimetry (DSC) and polarizing microscopy (PM) at different temperatures. The employed PEG 400-water proportions were: 0-25-50% and 75% of polymer. A complete phase diagram was determined for each PEG 400-water mixture. A cubic mesophase and two (probably three) lamellar mesophases were detected in different regions of the phase diagrams. The addition of PEG 400 to the Asc16-water system shifts the limits of the liquid crystalline domains to lower temperature and surfactant concentration. At weight fraction of PEG 400≥50%, the limits of the domain of existence of cubic mesophase shift to low surfactant concentration compared with water-rich systems. The hydrated crystals are Asc16.2·6H(2)O. If the proportion of water is lower than that value, a mixture of hydrated and anhydrous crystals appears. Heating these crystals produce waxy crystals having melted hydrocarbon bilayers retaining their crystalline structure because the polar bilayers are still rigid., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The adsorption of the herbicide paraquat (PQ(2+)) on the binary system titania-silica has been studied in batch experiments by performing adsorption isotherms under different conditions of pH, supporting electrolyte concentration, and temperature. Adsorption kinetic on the studied material has also been carried out and discussed. PQ(2+) adsorption is very low on the bare silica surface but important on the composed TiO(2)-SiO(2) adsorbent. In this last case, the adsorption increases by increasing pH and decreasing electrolyte concentration. There are no significant effects of temperature on the adsorption. The increase of the adsorption in TiO(2)-SiO(2) seems to be related to an increase in acid sites of the supported titania and to the homogenously dispersion of the TiO(2) nanoparticles over the silica support. The adsorption takes place by direct binding of PQ(2+) to TiO(2) leading to the formation of surface species of the type SiO(2)-TiO(2)-PQ(2+). Electrostatic interactions and charge-transfer and outer-sphere complexes formations seem to play a key role in the adsorption mechanism. The analysis of thermodynamic parameters suggests that the adsorption on TiO(2)-SiO(2) is endothermic and spontaneous in nature., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Removal of the antibiotic tetracycline (TC) by TiO(2) and the mesoporous binary system TiO(2)-SiO(2) have been studied in batch experiments by performing adsorption isotherms/kinetics and photodegradation kinetics under different conditions of pH, supporting electrolyte concentration, temperature, adsorbent amount, and TiO(2)-loading. On the one hand, the adsorption of TC on the studied materials is strongly dependent on pH, increasing as pH decreases. The adsorption mechanism, controlled by diffusion processes, is strongly related to electrostatic attractions and H-bond formations mainly between amide, carbonylic and phenolic groups of the antibiotic and the functional groups of TiO(2). The adsorption capacity at constant pH increases in the order TiO(2)

A computational modeling (in gas phase) to study the disposition of the homologous surfactants in a bidimensional simple model of mixed and homogeneous micelles was performed for the case of R-trimethylammonium bromide surfactants with different linear R lengths from R = C(5) to C(17). First, the bidimensional homogeneous (one component) micelle was modeled, and as a second step, heterogeneous (two components) bidimensional micelles were modeled. The difference in the number of carbon atoms between hydrocarbon chains of the surfactants in the heterogeneous micelles, Δn(C), ranged from 2 to 8. Results were contrasted with experimental data obtained at our own laboratory. The exothermic values of the steric energy changes showed strong attraction between components of homologous surfactants mixture, especially when one of the surfactants has a long chain. It may be argued that the inclusion of a shorter surfactant in the mixture and the twisting of the longer surfactant makes the bidimensional arrangement formation more exothermic. All predictions were in agreement with previous experimental results.

The phase and rheological behavior of hexadecyl(trimethyl)azanium; 2-hydroxybenzoate (CTAS), and water as a function of surfactant concentration and temperature are investigated here. The critical micellization concentration (cmc(1)) and the concentration at which the structure of aggregates changes (cmc(2)) as well as the Krafft temperature (T(K)) are reported. A large micellar solution region exhibiting high viscosity, as well as hexagonal- and lamellar-phase regions were identified. In the dilute region, below the overlapping entanglement concentration (C*), the micellar solutions exhibit shear thickening. Above C*, wormlike micelles form and the solutions show strong viscoelasticity with Maxwell behavior in the linear regime and shear banding flow in the non-linear regime. The linear viscoelastic regime was analyzed with the Granek-Cates model, showing that the relaxation is controlled by the kinetics of reformation-and-scission of the micelles. The steady response in the non-linear regime is compared with the predictions of the Bautista-Manero-Puig (BMP) and the Giesekus models., (Copyright 2010 Elsevier Inc. All rights reserved.)

The dependence of the aggregation number (N(agg)) on composition and concentration of sodium oleate-cetyltrimethylammonium bromide mixed micelles as revealed by cyclic voltammetry experiments shows a complex relationship with the total concentration and the composition of surfactant mixtures. This behavior is related to the evolution with composition of the HLB values and with the composition and the excess free energy of mixed micellization, and is explained by the inclusion of the double bonds of oleate chains in the micellar Stern layers. The increase in size probably leads to a reduction of the micelle surface available for the polar headgroups, causing a reduction in the proportion of double bonds in the hydrocarbon-water interface and a change in the mixed micelle composition. Therefore, the generally held supposition that the composition of mixed micelles does not change with concentration seems rather unrealistic., (Copyright 2010 Elsevier Inc. All rights reserved.)

Amiodarone aqueous systems at concentrations C

The physicochemical and elastic properties of Langmuir mixed monolayers composed by dehydrocholic acid (HDHC) and didodecyldimethylammonium bromide (DDAB) were evaluated. The experiments were performed with a constant surface pressure penetration Langmuir balance based on Axisymmetric Drop Shape Analysis (ADSA). The behavior of such amphiphiles in monolayer was clearly non-ideal and would be seriously influenced by the amount of HDHC molecules present. The presence of bile acid type molecules caused the monolayer be more condensed (A(c) diminution) and the intermolecular attractive interactions be stronger (high epsilon(0) values). This fact would be related to H-bond formation between water and carboxilate and carbonile groups in the cholesteric ring and agreed with the existence of laterally structured microdomains at the monolayer (determined by the analysis of the first virial coefficient, b(0)<1, of the state equation). The miscibility of both surfactants in the monolayer, their high bulk hydrophobicity (pi(c)>35 mJ m(-2)) just with the obtained negative values of the free energy of mixing Delta G(mix), and the excess second virial coefficient (b(1))(E) obtained allows us to infer that net attractive interaction existed between HDHC and DDAB molecules at the monolayer and that mixed systems would be able to be used in the formulation of supramolecular assemblies.

Hexadecyltrimethylammonium bromide (C(16)TAB)-sodium perfluorooctanoate (C(8)FONa) and hexadecylpyridynium bromide (C(16)PyB)-C(8)FONa catanionic semifluorinated mixtures have been studied by conductivity, dynamic light scattering (DLS), cryo-transmission electron microscopy (cryo-TEM) and polarizing microscopy. The regular solution theory, applicable for a limited fluorinated molar ratio, does not predict long-range electrostatic interactions. The results are consistent with the fact that in the hydrogenated-rich region the interaction is attractive in both catanionic mixtures. The systems containing pyridinium headgroups were of the stronger interaction. A transition from micelles was found in both mixtures as a function of fluorinated molar ratio. Special attention was devoted to the effect of the head group in the system properties. The information related with the mean vesicle radius measured by DLS was compared with the vesicle size distribution as well as the elastic properties of the bilayer measured with cryo-TEM.

In this work, the aim was to evaluate the remotion (adsorption plus degradation) of two reactive dyes, Methylene Blue (MB) and Benzopurpurin (BP), from aqueous solutions by the utilization of TiO2-chitosan microporous materials. Two different TiO2-chitosan hybrid materials were synthesized: TiO2-Chit A with 280 mg chitosan/gTiO2 and TiO2-Chit B with 46.76 mg chitosan/g TiO2. Adsorption data obtained at different solution temperatures (25, 35, and 45 degrees C) revealed an irreversible adsorption that decrease with the increment of T. Langmuir, Freundlich and Sips isotherm equation were applied to the experimental data. The obtained parameters and correlation coefficient showed that the adsorption of both dyes on TiO2-Chit A at the three work temperatures was best predicted by the Langmuir isotherm, while Sips equation adjusted better to adsorption data on TiO2-Chit B. The adsorption enthalpy was relatively high and varied with T, indicating that interaction between adsorbent and adsorbate molecules was not only physical but chemical. There is a change in the adsorption heat capacity, (Delta(ads)C(p)<0), related with intense hydrophobic interactions. The kinetic adsorption data were processed by the application of Lagergren and Avrami models. It was found that adsorption of both dyes on both adsorbents under the operating conditions was best predicted by Avrami model. The variation of kinetic order, n, and k(av) with T are related to a pore followed by intra particle diffusion control of the adsorption rate. MB photodegradation on both TiO2-chitosan hybrid materials was of 91 (in A) and 41% (in B) and augmented with the chitosan content. For BP can be seen that the process in darkness resulted in a high remotion capacity than in UV light presence.

Bile acids (deoxycholic and dehydrocholic acids) spread mixed monolayers behavior at the air/water interface were studied as a function of subphase pH using a constant surface pressure penetration Langmuir balance based on the Axisymmetric Drop Shape Analysis (ADSA). We examined the influence of electrostatic, hydrophobic and hydration forces on the interaction between amphiphilic molecules at the interface by the collapse area values, the thermodynamic parameters and equation of state virial coefficients analysis. The obtained results showed that at neutral (pH=6.7) or basic (pH=10) subphase conditions the collapse areas values are similar to that of cholanoic acid and consistent with the cross-sectional area of the steroid nucleus (approximately 40 A(2)). The Gibbs energy of mixing values (DeltaG(mix)<0) and the first virial coefficients of the equation of state (b(0)<1) indicated that a miscible monolayer with laterally structured microdomains existed. The aggregation number (1/b(0)) was estimated within the order of 6 (pH=6.7) and 3 (pH=10). At pH=3.2, acidic subphase conditions, no phase separation occurs (DeltaG(mix)<0) but a high expanded effect of the monolayer could be noted. The mixed monolayer behavior was no ideal and no aggregates were formed (b(0)> or =1). Such behavior indicates that the polar groups of the molecules interacts each other more strongly by repulsive electrostatic forces than with the more hydrophobic part of the molecule.

Inverse gas chromatography (IGC) has been used to measure the interaction parameter between two twin-tailed cationic surfactants. Didodecyldimethylammonium (DDAB) and dioctadecyldimethylammonium (DODAB) bromides and their mixtures were used as stationary phases. IGC and DSC techniques have been used for the determination of the temperature zone of working. The activity coefficients at infinite dilution (on a mole fraction basis) were calculated for eleven probe solutes on each pure surfactant column. Values of interaction parameter between surfactants obtained at four weight fractions of the mixtures and at five temperatures are positive and suggested that the interactions is more unfavourable with the increment of DODAB concentration in the mixture. The results are interpreted on the basis of partial miscibility between DDAB and DODAB.

The behavior of the sodium dehydrocholate (NaDHC)-sodium deoxycholate (NaDC) mixed system was studied by a battery of methods that examine effects caused by the different components of the system: monomers, micelles, and both components. The behavior of the mixed micellar system was studied by the application of Rubingh's model. The obtained results show that micellar interaction was repulsive when the aggregates were rich in NaDHC. The gradual inclusion of NaDC in micelles led to a structural transformation in the aggregates and the interaction became attractive. The bile salts' behavior in mixed monolayers at the air-solution interface was also investigated. Mixed monolayers are monotonically rich in NaDC, giving a stable and compact adsorbed layer. Results have shown that the interaction in both micelles and monolayer is not ideal and such behavior is assumed to be due to a structural factor in their hydrocarbon backbone.

The aqueous mixed system decyltrimethylammonium bromide (C(10)TAB)-hexadecyltrimethylammonium bromide (C(16)TAB) was studied by conductivity, ion-selective electrodes, surface tension, and fluorescence spectroscopy techniques. The mixture critical micelle concentration, cmc(*), aggregation number, N( *), and micelle molar conductivity, Lambda(M)(cmc), showed that the system aggregation is strongly nonideal. Both cmc(*) and N( *) results were analyzed with two different procedures: (i) the regular solution theory on mixed micelles or Rubingh's theory, and (ii) by the determination of the partial critical micelle concentration of the amphiphile component i in the presence of a constant concentration of the other amphiphile component, cmc(i)( *). The Rubingh procedure gives micelles richer in C(16)TAB than the overall mixtures, while procedure (ii) gives micelles having the same composition as in the complete surfactant mixture (alpha(C(10)TAB). Mixed micelles are larger than pure surfactant ones, with nonspherical shape. Using a literature model, the cause of the synergistic effect seems to be a reduction of the hydrocarbon/water contact at the micelle surface when mixed micelles form. Conductivity and ion-selective electrodes indicate that highly ionized premicelles form immediately before the cmc(*). The air/solution interface is strongly nonideal and much richer in C(16)TAB than the composition in the bulk. When micelles form there is a strong desorption from the air/solution interface because micelles are energetically favored when compared with the monolayer.

The micellization of an aqueous mixture of sodium dodecanoate (SDD) and sodium 10-undecenoate (SUD) was studied with the theory of mixed micellization. A strong nonideality was found, with a preferential composition of mixed micelles. This phenomenon was interpreted on the basis of the interaction between the vinyl group and water by hydrogen bonding. The importance of the aliphatic pi electrons and water was stated.

The interaction between sodium perfluorooctanoate (SPFO) and dodecyltrimethylammonium bromide (DTAB) was studied by several methods and it was found strongly synergistic. Above a mole fraction of SPFO in the surfactant mixture (alpha(SPFO))=0.38, the interaction is repulsive and increases with the content of SPFO in both, the overall mixture and micelles, whereas the interaction is attractive if DTAB is in excess. At alpha(SPFO)=0.38 the low miscibility between hydrocarbon and fluorocarbon is counterbalanced by the electrostatic attraction between the opposite charged head groups, and the micelle composition is ideal (i.e., the mole fraction of SPFO in micelles X(SPFO)=alpha(SPFO)=0.38). The solubility of fluorocarbon in hydrocarbon is lower than that of hydrocarbon in fluorocarbon. Micelles of DTAB act as a solvent for SPFO without important structural changes, whilst micelles of SPFO undergo important changes when dissolve DTAB. This asymmetry may be interpreted as caused by the difference in chain length that favors the inclusion of the shorter chain in micelles of the longer surfactant, but disfavors the opposite process. Above X(SPFO)=0.5 there is an excess adsorption of bromide ions on the mixed micelles surface, giving rise to a high zeta potential. Micelles of pure SPFO or pure DTAB show an important energy barrier which prevents micelle flocculation. The inclusion of SPFO in DTAB micelles produces a reduction of the energy barrier, which disappeared when alpha(SPFO)=0.5. This produces the flocculation of micelles giving rise to the formation of a non-birefringent coacervate, which is probably formed by unordered isometric clusters of micelles.

The phase and rheological behaviors of the polymerizable surfactant, cetyltrimethylammonium benzoate (CTAVB), and water as a function of surfactant concentration and temperature are investigated here. The critical micelle concentration (cmc) and the (cmc(2)), as well as the Krafft temperature (T(K)), are reported. A large highly viscous micellar solution region and hexagonal- and lamellar-phase regions were identified. The micellar solutions exhibit shear thickening in the dilute regime, below the overlapping or entanglement concentration. At higher concentrations, wormlike micelles form and the solutions show strong viscoelasticity and Maxwell behavior in the linear regime and shear banding flow in the nonlinear regime. The linear viscoelastic regime is analyzed with the Granek-Cates model, showing that the relaxation is controlled by the kinetics of reformation and scission of the micelles. The steady and unsteady responses in the nonlinear regime are compared with the predictions of the Bautista-Manero-Puig (BMP) model. Model predictions follow the experimental data closely.

The effects of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) on the electrochemical behavior of iron were studied by potentiodynamic and potentiostatic techniques and open-circuit potential measurements. Experiments were made in both neutral and alkaline AOT solutions (pH 7 and pH 12). It was found that AOT-assisted dissolution is initiated on a passivated iron surface and that the oxidation current leads to the formation of a gel-like film on the electrode surface. This dissolution process was investigated as a function of pH, potential, and electrode rotation rate and the corrosion products were characterized by polarizing microscopy, SEM/EDX, and IR spectroscopy. The gel-like material is a mixed NaAOT-Fe(AOT)3 lamellar mesophase and a structure for this mesophase is proposed.

The interaction between homologous surfactants in mixed micelles was studied by the Regular Solution Theory of mixed micelles. The interaction is independent of the nature of the polar head groups and attractive and the interaction parameter betaM depends linearly on the difference in chain length DeltanC. The interaction becomes ideal at DeltanC=0.75+/-0.06. Above DeltanC approximately 5, the dependence remains linear but the slope increased 2.7 times. The phenomenon is explained as the effect of the reduction of the hydrocarbon/water micelle interface and a better packing of the chains in the micelle core, caused by the inclusion of a shorter homologous surfactants. This reduction can be more effective when DeltanC>or=5.

The mixed surfactant system sodium 10-undecenoate (SUD)-dodecyltrimethylammonium bromide (DTAB) was studied by computational simulation to determine the composition and structure of the mixed microstructures. Results were contrasted with experimental data obtained from literature and our own laboratory. The modelization predicts spherical or cylindrical micelles with a preferential composition of SUD-DTAB of about 1:2, while the system predicts a lamellar structure with a proportion of 1:1 when SUD is replaced by the saturated soap sodium undecanoate. The model also predicts the deep inclusion of bromide ions in the micelle Stern layer. All predictions were in agreement with previous experimental results.

Titania mesosized particles were obtained by TiCl4 hydrolysis in Aerosol OT/water/n-hexane microemulsion. These particles were incorporated in surfactant templated silica mesoporous materials of MCM-41 and MCM-50 structures. Results depended on the surfactant: hexadecyltrimethylammonium bromide templated materials retained the honeycomb structure with small modifications in their characteristics. The dodecyltrimethylammonium bromide templated material changed from honeycomb to lamellar structure when the titania particles were included, with dramatic changes in the structure characteristics. The didodecyldimethylammonium bromide templated lamellar structure was retained after TIO2 inclusion, with a slight increase in the specific area, pore diameter and pore walls thickness.

This paper presents a study on the adsorption of two basic dyes, methylene blue (MB) and rhodamine B (RhB), from aqueous solution onto mesoporous silica-titania materials. The effect of dye structure, adsorbent particle size, TiO(2) presence, and temperature on adsorption was investigated. Adsorption data obtained at different solution temperatures (25, 35, and 45 degrees C) revealed an irreversible adsorption that decreased with the increment of T. The presence of TiO(2) augmented the adsorption capacity (q(e)). This would be due to possible degradation of the dye molecule in contact with the TiO(2) particles in the adsorbent interior. The adsorption enthalpy was relatively high, indicating that interaction between the sorbent and the adsorbate molecules was not only physical but chemical. Both Langmuir and Freundlich isotherm equations were applied to the experimental data. The obtained parameters and correlation coefficients showed that the adsorption of the two reactive dyes (MB and RhB) on the adsorbent systems at the three work temperatures was best predicted by the Langmuir isotherm, but not in all cases. The kinetic adsorption data were processed by the application of two simplified kinetic models, first and second order, to investigate the adsorption mechanism. It was found that the adsorption kinetics of methylene blue and rhodamine B onto the mesoporous silica-titania materials surface under different operating conditions was best described by the first-order model.

Conductivity, density, and sound velocity measurements as functions of temperature were made on tetraethylammonium perfluorooctylsulfonate solutions to determine the Krafft point, the dependence on temperature of the critical micelle concentration, the micellar ionization degree, and several thermodynamic properties: Gibbs free energy, enthalpy and entropy of micellization, apparent molar partial volume, thermal expansion coefficient, and the adiabatic compressibility factor of both micellized and unmicellized surfactants. Important changes occur at about 30 degrees C. Results are interpreted on the basis of dehydration of surfactant on micellization and on temperature increase.

The aggregation characteristics of tetraethylammonium perfluorooctylsulfonate in water were studied by several techniques: conductivity, pH, ion-selective electrodes, and surface tension. It was concluded that the aggregation process is gradual and starts with the formation of oligomers such as ion pairs that grow to give spherical micelles, which become wormlike with increasing concentration. Because of the size and hydrophobicity of the counterion, micelles quickly increase in ionization degree up to about 0.5. Differences among different critical micelle concentration values in the literature are explained on the basis of the gradual formation of micelles.

We describe a patient with recurrence of Hodgkin's disease and severe liver disease of unknown origin in whom autoimmune neutropenia developed. Because of possible seronegative viral hepatitis he was treated with high-dose intravenous immunoglobulin instead of steroids. He responded with a prompt but transitory increase of the neutrophil count and recovered completely after chemotherapy.

For effective treatment of coronary heart disease with calcium antagonists, knowledge of both the dose-response relationship of a remedy and equipotent dosage for comparison of different drugs is necessary. We performed controlled studies to evaluate the influence of single oral doses of calcium antagonists on ischemic ST-depression (calculated as the mean of all exercise and recovery minutes = mean ST-depression) in exercise ECGs of patients with proven CHD and stable angina pectoris. Ergometries were carried out under constant conditions, particularly with individually constant work load and duration. All calcium antagonists reduced ischemic ST-depression during ergometry dose-dependent when compared to placebo. Diltiazem: 90 mg: 6% (n.s.), 120 mg: 19% (n.s.) und 180 mg: 26% (p less than 0.025); gallopamil: 25 mg: 19% (n.s.), 50 mg: 34% (p less than 0.01) und 100 mg: 57% (p less than 0.0025); nifedipine-Cps.: 5 mg: 17%, 10 mg: 33% und 20 mg: 42%; nifedipine-Tbl.: 20 mg: 8% (p less than 0.05), 40 mg: 23% (p less than 0.057 und 60 mg: 31% (p less than 0.05); tiapamil: 300 mg: 30% (p less than 0.05) und 600 mg: 60% (p less than 0.01). As the result of our findings, comparable antiischemic effects can be expected with 120 mg diltiazem, 50 mg gallopamil, 20 mg nifedipin as capsule or 60 mg nifedipin as tablet and 600 mg tiapamil.