Determination of interfacial co-ion concentration in ionic micelles by chemical trapping: Halide concentration at the interface of sodium dodecyl sulfate micelles

Products from the spontaneous reaction of a long-chain arenediazonium salt, 2,6-dimethyl-4-hexadecylbenzenediazonium tetrafluoroborate(16-ArN2BF4), in aqueous micellar solutions of sodium dodecyl sulfate (SDS)? are used to estimate the local concentration of chloride and bromide ions at the micellar surface. The arenediazonium ion, 16-ArN2+, which is totally bound to the SDS micelle, reacts by rate-determining loss of N-2 to give an aryl cation that traps available nucleophiles, i,e., H2O, Cl-, and Br-, to give stable phenol, 16-ArOH, and halobenzene products, 16-ArCl and 16-ArBr, respectively. Product yields, determined by HPLC, are related to local concentrations using calibration curves obtained from independent standards. The local concentrations determined by this method are consistent with co-ion concentrations calculated, using a cell model, by numerical integration of the Poisson-Boltzmann equation (PBE) taking into account salt-induced micellar growth. The salt dependence of the intel facial concentrations of Cl- and Br- are identical. indicating no specific interactions in the interfacial co-ion compartment. PBE calculations predict that, in micellar SDS, increasing the concentration of a particular halide salt (NaX) at constant concentration of another halide (NaY) should result in an increase in the local concentrations of both co-ions. Using this chemical-trapping method, this prediction was demonstrated experimentally.

Mixed micelles of the anionic surfactant sodium dodecyl sulfate and the nonionic pentaethylene glycol mono-n-dodecyl ether in solution

Dynamic light scattering, surface tension, and clouding temperature have been monitored to elucidate the solution properties of mixed micelles formed between the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant pentaethylene glycol mono-n-dodecyl ether (C12E5) over a wide range of surfactant concentration and temperature. Addition of 0.1 M NaCl shifts the relaxational modes to higher frequency and lowers the clouding temperature (T-c) of the nonionic surfactant solution by about 1 degrees C compared to the salt-free system. T-c for the mixed surfactant solutions is higher than that of the binary C12E5 solutions and depends sensitively on the concentration of the two surfactants but increases only slightly when the total surfactant concentration is increased at a given molar C12E5/SDS concentration ratio. With C12E5/SDS = 5.7, for example, T-c is 46.0 and 47.5 degrees C, respectively, at 5 and 70 mM of C12E5 the mixed solutions are homogeneous and stable and contain nonspherical micelles, which are close to monodisperse over a range of surfactant concentrations and temperature. The mixed system has a lower Krafft point than binary SDS solutions and shows an approximately ideal behavior in contrast to the binary C12E5 solution. The hydrodynamic radius (RH) of the mixed micelle increases with temperature as do C12E5 micelles in the binary solutions and also with increasing C12E5/SDS ratio. At 25 degrees C, the critical micelle concentration of the mixed solution lies between those of the individual surfactants and decreases as the C12E5/SDS ratio is increased.

pH at the micellar interface: Synthesis of pH probes derived from salicylic acid, acid-base dissociation in sodium dodecyl sulfate micelles, and Poisson-Boltzmann simulation

The study of the H+ concentration at the micellar interface is a convenient system for modeling the distribution of H+ at interfaces. We have synthesized salicylic acid derivatives to analyze the proton dissociation of both the carboxylic and phenol groups of' the probes, determining spectrophotometrically the apparent pK(a)'s (pK(ap)) in sodium dodecyl Sulfate, SDS, micelles with and without added salt. The synthesized probes were 2-hydroxy-5-(2-trimethylammoniumacetyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumacetyl)benzoate- 2-hydroxy-5-(2-dimethylhexadecylammoniumhexanoyl)benzoate-, 2-hydroxy-5-(2-diniethylhexadecylammoniumundecanoyl)betizoate; 2-hydroxy-5-acetylbenzoic acids and 2-hydroxy-5-dodecanoylbenzoic acid. Upon incorporation into SDS micelles the pK(ap)'s of both carboxylic and phenol groups increased by ca. 3 pH units and NaCl addition caused a decrease in the probe-incorporated pKap. The experimental results were fitted with a cell model Poisson-Boltzmann (P-B) equation taking in consideration the effect of salt on the aggregation number of SDS and using the distance of' the dissociating group as a parameter. The conformations of the probes were analyzed theoretically using two dielectric constants, e.g., 2 and 78. Both the P-B analysis and conformation calculations can be interpreted by assuming that the acid groups dissociate very close to, or at, the interface. Our results are consistent with the assumption that the intrinsic pK(a)'s of both carboxylic and phenol groups of the salicylic acid probes used here can be taken as those in water. Using this assumption the micellar and salt effects on the pKap's of the (trialkylammonium)benzoate probes were described accurately using a cell model P-B analysis. (c) 2005 Elsevier B.V. All rights reserved.

Structural features of phosphate and sulfate modified zirconia prepared by sol-gel route

This paper describes the effect of sulfate, phosphate and nitrate complexing ligands on the structural features of amorphous xerogels and on the crystallization of metastable zirconia phases during the xerogel-ceramic conversion. Powdered samples were prepared by a sol-gel route using zirconyl chloride precursors chemically modified by complexing ligands. The structural evolution of ZrO2 phases as function of firing temperature was analyzed by XRPD, EXAFS and P-13 NMR/MAS. The experimental results show the formation of metastable t-ZrO2 during the low firing temperature of xerogels modified by sulfate or phosphate groups. The martensitic tetragonal-monoclinic transformation occurs during desorption of sulfate groups. The largest temperature interval of stability of metastable tetragonal zirconia was observed for phosphate-modified xerogels.

INCREASED CALCIUM AFFINITY OF A FUCOSYLATED CHONDROITIN SULFATE FROM SEA-CUCUMBER

Calcium binding and charge distribution on a fucosylated chondroitin sulfate and a standard chondroitin 6-sulfate have been studied using a metallochromic indicator and conductimetric titrations. The fucosylated chondroitin sulfate has a similar to 5-fold greater affinity for calcium ions than the standard chondroitin 6-sulfate. Possibly, this increased affinity for calcium ions is due to the branches on the fucosylated chondroitin sulfate, since the calcium affinity of an unbranched, sulfated fucan is similar to that of the standard chondroitin 6-sulfate. More charged groups per disaccharide unit (and a shorter distance between these groups) also distinguish the fucosylated chondroitin sulfate from standard chondroitin 6-sulfate. Comparison between native and chemically modified (desulfated or carboxyl-reduced) polysaccharides suggests that the sulfate esters are responsible for the increased charge density of the fucosylated chondroitin sulfate and that the presence of the fucose branches does not alter the length of the repetitive units which compose the central core of chondroitin from sea cucumber. These results are consistent with the chemical studies of these two polysaccharides.

Thermostimulated sol-gel transition in suspensions of sulfate zirconium oxychloride

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Indirect determination of chloride and sulfate ions in alcohol fuel by capillary electrophoresis

A capillary zone electrophoresis method using indirect UV detection for the analysis of chloride and sulfate in alcohol fuel samples was developed. The anions were analyzed in less than 3 min using an electrolyte containing 10 mmol 1(-1) chromate and 0.75 mmol 1(-1) hexamethonium bromide (HMB) as electroosmotic flow modifier. Coefficients of variation were better than 0.6% for migration time (n = 10) and between 2.05 and 2.82% for peak area repeatabilities. Analytical curves of peak area versus concentration in the range of 0.065-0.65 mg kg(-1) for chloride and 0.25-4.0 mg kg(-1) for sulfate were linear with coefficients of correlation higher than 0.9996. The limits of detection for sulfate and chloride were 0.033 and 0.041 mg kg(-1), respectively. Recovery values ranged from 85 to 103%. The method was successfully applied for the quantification of sulfate and chloride in five alcohol fuel samples. The concentration of sulfate varied from 0.45 to 3.12 mg kg(-1). Chloride concentrations were below the method's LOD.

Rheological study of the thermoreversible sol-gel transition of sulfate modified zirconyl chloride aqueous sol

The sols prepared by mixing a ZrOCl2 acidified solution to a hot H2SO4 aqueous solutions were studied in order to clarify the mechanism of thermoreversible sol-gel transition observed in this system. The viscoelastic properties of these suspensions were analyzed during the sol-gel transition by dynamic rheological measurements and quasi-elastic light scattering. The rheological properties were correlated to mass fractal and nearly linear growth models, and percolation theory. The results evidence that the thermoreversible sol-gel transition in this system is due to the formation of a network of physically linked aggregates having fractal structure. The decrease of the SO42- contents in the initial solution leads to the decrease of the fractal dimensionality from 2.3 to 1.8, indicating a change of the kinetic mechanism of aggregate growth. Near the gel point these samples have the typical scaling expected from percolation theory. (C) 2004 Elsevier B.V. All rights reserved.

Electrochemical behavior of cobalt oxide coatings on cold-rolled steel in alkaline sodium sulfate

The electrochemical behavior of a coating of cobalt oxide on cold-rolled steel in alkaline sodium sulfate was Studied using the electrochemical techniques of open-circuit potential measurements and electrochemical impedance spectroscopy. The coating was prepared at different annealing temperatures ranging from 350 to 750 degreesC and characterized by SEM, EDX and XRD. Below 550 degreesC the composition of the coating was basically of Co3O4. At 750 degreesC CoO was formed and big cracks appeared on the film exposing an inner layer of iron oxides. Analysis of the EIS data is very difficult because of the complexity of the interface structure. It can be inferred that the charge transfer resistance of the coatings prepared at 350 and 450 C were higher than those for the coatings prepared at temperatures above 550 degreesC. (C) 2002 Published by Elsevier B.V. Ltd.

Stimuli-responsive controlled growth of mono- and bidimensional particles from basic zirconium sulfate hydrosols

A thermostimulated sol-gel transition in a system prepared by mixing a ZrOCl(2) acidified solution to a hot H(2)SO(4) aqueous solution was studied by dynamic theological measurements and quasi-elastic light scattering. The effect of temperature and of molar ratio R(S) = [Zr]/[SO(4)] on the gelation kinetics was analyzed using the mass fractal aggregate growth model. This study shows that the linear growth of aggregates occurs at the early period of transformation, while bidimensional growth occurs at the advanced stage. The bidimensional growth can be shifted toward monodimensional growth by decreasing the aggregation rate by controlling the temperature and/or molar ratio R(S). EXAFS and Raman results gave evidence that the linear chain growth is supported by covalent sulfate bonding between primary building blocks. At the advanced stage of aggregation, the assembly of linear chains through hydrogen bonding gave rise to the growth of bidimensional particles.

EFEIFOS DO SULFATE DE MAGNESIO NA HEMODINAMICA CARDIOVASCULAR DE CAES ANESTESIADOS COM PENTOBARBITAL SODICO

Background and Objectives - A controversy exists in the literature regarding the effects of the acute administration of magnesium on the cardiovascular system of animals and humans. The purpose of this study was to evaluate the effects of hypermagnesemia on the cardiovascular hemodynamics of dogs. Methods - Sixteen mongrel dogs were anesthetized with pentobarbitone 30 mg.kg-1 and submitted to volume expansion with Ringer's solution (0.4 ml.kg-1.min-1 and mechanical ventilation with room air. In this model, the hemodynamic repercussions of the following drugs and doses were studied. pentobarbitone 5 mg.kg-1 Group 1, control - and the association of pentobarbitone and magnesium sulphate (MS), at the dose of 140 mg.kg-1 injected in 15 minutes, followed by an infusion of 80 mg.kg-1.h-1 - Group 2. The parameters studied were: heart rate, blood pressure, inferior vena cava pressure, cardiac index, systolic index and peripheral resistance index, evaluated at 5 different moments: 15(M1), 30(M2), 60(M3) and 75(M4) minutes after the first suppplementary dose of pentobarbitone and 15 minutes (M5) after the second supplementary dose. In Group 2, the moments M3, M4, M5 corresponded to 15, 30 and 60 minutes after the priming dose of magnesium sulphate. Results - Group 1 animals exhibited tachycardia since the beginning of the experiment. There was a decrease in the cardiac index, in the systolic index and an increase in the inferior vena cava pressure. Group 2 animals also exhibited tachycardia, but heart rate decreased after MS infusion. The blood pressure and the peripheral resistance index decreased. The systolic index increased and the cardiac index decreased only at the end of the experiment. Conclusions: The antiadrenergic effects of MS could have been responsible for the decrease in heart rate. The vasodilating effects of the magnesium induced the decrease in the peripheral resistance index. The systolic index increased, showing that myocardial depression did not occur.

EFEITOS DO SULFATE DE MAGNESIO NA HEMODINAMICA E FUNCAO RENAL DE CAES ANESTESIADOS CORN PENTOBARBITAL SODICO

Background and objectives - The use of magnesium sulphate for the prevention of seizures in pre-eclampsia may induce hypermagnesemia. Clinical and experimental studies are not in agreement about the effects of magnesium on the renal hemodynamics and function. We therefore studied the effects of hypermagnesemia on the renal hemodynamics and function of dogs anesthetized with pentobarbitone. Methods - Sixteen mongrel dogs were anesthetized with pentobarbitone 30 mg.kg-1 and submitted to extracellular ) and mechanical ventilation with room air. The dogs were volume expansion with Ringer's solution (0.4 ml.kg.min allocated into two groups of 8 animals, for the study of renal hemodynamics and function following the administration of 5 mg.kg-1 of pentobarbitone (Group 1 - control or of pentobarbitone associated with magnesium sulphate in the dose (Group 2). The parameters studied were: PAH of 140 mg.kg, administered in 15 minutes, followed by 80 mg.kg-1.h-1 clearance, creatinine clearance, osmolar clearance, free water clearance, renal blood flow, renal vascular resistance, filtration fraction, urinary volume, plasmatic and urinary osmolarity, urinary and fractionary excretion of sodium and potassium, measured at five moments: 15 (M1), 30 (M2), 60 (M3) and 75 (M4) minutes after the first supplementary dose of pentobarbitone and 15 minutes (M5) after the second supplementary dose in Group 1. In Group 2, the moments M3, M4, M5 were 15, 30 and 60 minutes after the priming dose of magnesium sulphate and during the maintenance dose. Results - In Group I no significant changes were observed in renal hemodynamic parameters and creatinine clearance. The extracellular volume expansion increased urinary volume and decreased urinary osmolarity as a consequence of sodium, potassium and free water clearance. The fractionary excretion of sodium was maintained. The plasmatic osmolarity increased. In Group 2, renal hemodynamic parameters and creatinine clearance were also maintained. There was an increase in renal sodium clearance, as detected by the increase in the fractionary excretion of sodium. Conclusions - Magnesium sulphate did not produce significant changes in renal hemodynamics and facilitated the renal excretion of sodium in dogs anesthetized with pentobarbitone.

Bone healing in surgically created defects treated with either bioactive glass particles, a calcium sulfate barrier, or a combination of both materials: A histological and histometric study in rat tibias

Objective: The purpose of this study was to histologically analyze the influence of bioactive glass and/or a calcium sulfate barrier on bone healing in surgically created defects in rat tibias. Material and methods: Sixty-four rats were divided into 4 groups: C (control), CS (calcium sulfate), BG (bioactive glass), and BG/CS (bioactive glass/calcium sulfate). A surgical defect was created in the tibia of each animal. In Group CS, a calcium sulfate barrier was placed to cover the defect. In Group BG the defect was filled with bioactive glass. In Group BG/CS, it was filled with bioactive glass and protected by a barrier of calcium sulfate. Animals were sacrificed at 10 or 30 days post-operative. The formation of new bone in the cortical area of the defect was evaluated histomorphometrically. Results: At 10 days post-operative, Group C presented significantly more bone formation than Groups CS, BG, or BG/CS. No statistically significant differences were found between the experimental groups. At 30 days post-operative, Group C demonstrated significantly more bone formation than the experimental groups. Groups CS and BG/CS showed significantly more bone formation than Group BG. No statistically significant differences were found between Group CS and BG/CS. Conclusions: (a) the control groups had significantly more bone formation than the experimental groups; (b) at 10 days post-operative, no significant differences were found between any of the experimental groups; and (c) at 30 days post-operative, the groups with a calcium sulfate barrier had significantly more bone formation than the group that used bioactive glass only. Copyright © Blackwell Munksgaard 2005.

Autogenous bone graft with or without a calcium sulfate barrier in the treatment of class II furcation defects: A histologic and histometric study in dogs

Background: The purpose of this study was to histologically evaluate the healing of surgically created Class II furcation defects treated using an autogenous bone (AB) graft with or without a calcium sulfate (CS) barrier. Methods: The second, third, and fourth mandibular premolars (P2, P3, and P4) of six mongrel dogs were used in this study. Class II furcation defects (5 mm in height × 2 mm in depth) were surgically created and immediately treated. Teeth were randomly divided into three groups: group C (control), in which the defect was filled with blood clot; group AB, in which the defect was filled with AB graft; and group AB/CS, in which the defect was filled with AB graft and covered by a CS barrier. Elaps were repositioned to cover all defects. The animals were euthanized 90 days post-surgery. Mesio-distal serial sections were obtained and stained with either hematoxylin and eosin or Masson's trichrome. Histometric, using image-analysis software, and histologic analyses were performed. Linear and area measurements of periodontal healing were evaluated and calculated as a percentage of the original defect. Percentage data were transformed into arccosine for statistical analysis (analysis of variance; P<0.05). Results: Periodontal regeneration in the three groups was similar. Regeneration of bone and connective tissue in the furcation defects was incomplete in most of the specimens. Statistically significant differences were not found in any of the evaluated parameters among the groups. Conclusion: Periodontal healing was similar using surgical debridement alone, AB graft, or AB graft with a CS barrier in the treatment of Class II furcation defects.

Bone healing in critical-size defects treated with bioactive glass/calcium sulfate: A histologic and histometric study in rat calvaria

Objective: The purpose of this study was to analyze histologically the influence of bioactive glass (BG) with or without a calcium sulfate (CS) barrier on bone healing in surgically created critical-size defects (CSD) in rat calvaria. Material and methods: A CSD was made in each calvarium of 48 rats. They were divided into three groups: C (control): blood clot only; BG: defect filled with BG; and BG/CS: defect filled with BG covered by a CS barrier. Animals were euthanized at 4 or 12 weeks. Formation of new bone was evaluated histomorphometrically. Results: No defect completely regenerated with bone. BG particles were observed in Groups BG and BG/CS at both periods of analysis. The thickness throughout the healing area in Groups BG and BG/CS was similar to the original calvarium, while Group C presented a thin connective tissue in the center of the defect in both periods of analysis. At 4 weeks, Groups C and BG/CS presented significantly more bone formation than Group BG. No significant differences were found between Groups C and BG/CS. At 12 weeks, no significant differences in the amount of bone formation were observed among the three groups. When comparing 4 and 12 weeks, there was a significant increase in new bone formation within groups BG and BG/CS, but not C. Conclusion: BG particles, used with or without a CS barrier, maintained the volume and contour of the area grafted in CSD. However, they did not lead to a significant difference in bone formation when compared with control at 12 weeks post-operative. © 2007 Blackwell Munksgaard.