An investigation of the voltammetric characteristics of the osazone of dihydroxytartaric acid

Differential pulse polarography (d.p.p.), supplemented by other voltammetric techniques, is used to elucidate the tautomeric structures associated with buffered aqueous solutions of the osazone of dihydroxytartaric acid. In particular, d.p.p. is used to evaluate the number of electrons and protons associated with each of seven reduction processes, at pH values ranging from 2.5–11.5. The reversibility of the electrode processes is demonstrated by cyclic voltammetry and d.p.p. All the reduction processes studied are diffusion-controlled. Mechanisms for these reductions are proposed on the basis of the tautomeric equilibrium associated with the osazone in solution.     

An Analysis of the Interactions of BSA with an Anion-Exchange Surface Under Linear and Non-Linear Conditions

The interactions of BSA with an anion-exchange adsorbent have been studied to aid in the understanding of protein adsorption in ion-exchange chromatography. Linear chromatography, flow microcalorimetry and isotherm measurements were used to analyze adsorption energetics in the linear and overloaded regions of the equilibrium isotherm. The effects of salt type, salt and protein concentration, and temperature are reported. It was observed that under all conditions studied the adsorption process was entropically driven. This was contrary to expectations, since at the pH selected ion exchange is expected to dominate. A major driving force for the adsorption of BSA on the anion exchanger was concluded to be the increase in entropy from the release of water due to interactions between hydrophobic regions on the protein and adsorbent. The data further suggest that the conformational entropy change accompanying protein adsorption on the ion exchanger may also be significant.     

A study of the interaction between the osazone of dihydroxytartaric acid and calcium ions in alkaline solution using differential pulse polarography

Differential pulse polarography on osazone solutions of pH 11.4 to which excess calcium ions had been added has shown that, at low ionic strengths (I = 0.03 M), a 1:1 neutral complex forms between the osazone and calcium ions. A possible structure for the complex has been proposed.     

Thermodynamics of the lanthanum-hydrogen system at 917°K

The binary system lanthanum-hydrogen has been studied at pressures up to 1 atm at 917°K by a calorimetric-equilibrium method. From the calorimetric measurements we found the enthalpy of formation of LaH₂ at 917°K to be ?45.7 kcal mole^?1 with an estimated uncertainty at ±0.3 kcal mole^?1. This result is about 4 kcal mole^?1 less negative than the values derived indirectly from plateau pressure equilibrium measurements by Mulford and Halley and by Korst and Warf. A comparison between the calorimetric and equilibrium measurements at 917°K provides information on the partial entropy of hydrogen in lanthanum and in the dihydride LaH_2±δ. The excess entropy of hydrogen in lanthanum is about 6 cal K^?1 mole^?1 at 917°K: this value is essentially fully accounted for by the estimated vibrational entropy contribution of the hydrogen atoms. In LaH_2±δ the partial entropy of hydrogen changes from small negative values at X ≈ 1.95 to positive values for X > 2. This entropy change is explained by an assumed intrinsic disorder of hydrogen in LaH₂ of about 0.02.     

Fluorine-19 magnetic resonance in measurement of the thermodynamics of the reaction of o-alkylphenols with hexafluoroacetone

The reaction of several o-alkylphenols with hexafluoroacetone at 0-68 degrees was followed by measuring the fluorine magnetic resonance. A knowledge of the equilibrium of the hemiacetal formation is useful in devising schemes for determination of these compounds. The enthalpy and entropy changes for the equilibrium were found to become less negative with increasing size of the ortho-substituents, indicating the importance of steric interaction. The equilibrium data correlate well with Taft's constant and sigma(ortho) from pK(a), values, but deviate from sigma(-) derived from measurements of phenolic proton chemical shifts.     

The influence of temperature on the adsorption of mellitic acid onto goethite

The adsorption of mellitic acid (benzene-1,2,3,4,5,6-hexacarboxylic acid) onto goethite was investigated at five temperatures between 10 and 70 degrees C. Mellitic acid adsorption increased with increasing temperature below pH 7.5, but at higher pH the effect of increasing temperature was to reduce the amount adsorbed. Potentiometric titrations were conducted and adsorption isotherms were measured over the same temperature range, and the data obtained were used in conjunction with adsorption edge data to develop an Extended Constant Capacitance Surface Complexation Model of mellitic acid adsorption. A single set of reactions was used to model the adsorption for the three different experiment types at the five temperatures studied. The adsorption reactions proposed for mellitate ion (L(6-)) adsorption at the goethite surface (SOH) involved the formation of two outer-sphere complexes: SOH + L(6-) + 3H+ <==> [(SOH2)+ (LH2)(4-)]3-, 2SOH + L(6-) + 2H+ <==> [(SOH2)2(2+) (L)(6-)]4-. This mechanism is consistent with recent ATR-FTIR spectroscopic measurements of the mellitate-goethite system. Thermodynamic parameters calculated from the temperature dependence of the equilibrium constants for these reactions indicate that the adsorption of mellitic acid onto goethite is accompanied by a large entropy increase.     

Radiation grafting of ionically crosslinked alginate/chitosan beads with acrylic acid for lead sorption

Radiation-induced grafting of acrylic acid onto alginate/chitosan beads was performed in solution at a dose rate of 20.6 Gy/min of Co-60 gamma rays. The effect of absorbed dose on grafting yield was investigated. The characterization of the grafted and un-grafted beads was performed by FTIR spectroscopy and the swelling measurements at different pHs was studied. It is found that as the pH value increases the swelling degree increases up to pH 6 but with further increase in pH value the swelling decreases. Also, it is noticed that the grafting yield increased with increase the irradiation dose. Both un-grafted and grafted alginate/chitosan beads were examined as sorbents for the removal of Pb ions from aqueous solutions. The sorption behavior of the sorbents was examined through pH, and equilibrium measurements. Grafted alginate/chitosan beads presented higher sorption capacity for Pb ions than un-grafted beads.     

Studies on the riboflavin-resorcinol interaction in an aqueous medium and its pH dependence

The equilibrium constants, K', for the formation of the molecular association complex between riboflavin and resorcinol in the pH range 6-8 were found to be in the range 5-25 mol(-1)dm(3) by difference absorption spectroscopy. The equilibrium constants from emission spectroscopy were estimated to be in the range 38-55 mol(-1)dm(3) over the same pH range. Both sets of K' show a remarkable dependence on pH. The equilibrium constants K(A) and K(B) describing the interaction of riboflavin with neutral and ionic forms of resorcinol, respectively, obtained by resolving K', shows that K(B) is much greater than K(A). Molecular modeling studies suggest a stacked conformation of the two components in the complexed form. The interaction energies obtained from modeling studies also suggest a stronger interaction between the ionic form of resorcinol and riboflavin.     

Effect of molecular symmetry on melting temperature and solubility

Molecular symmetry has a pronounced effect on the melting properties and solubility of organic compounds. As a general rule, symmetrical molecules in crystalline form have higher melting temperatures and exhibit lower solubilities compared with molecules of similar structure but with lower symmetry. Symmetry in a molecule imparts a positive amount of residual entropy in the solid phase (i.e., more possible arrangements leading to the same structure). This means that the entropy of a crystal of symmetric molecules is greater than the entropy of crystal of a similar, but non-symmetric molecule. An analysis is presented relating the enthalpy, entropy and temperature of melting for an idealised system of structural isomers of different molecular symmetries. The analysis presented helps explain why often, yet not always, the crystal of a more symmetric molecule, which has greater entropy to start (closer to that of the liquid), also exhibits a greater gain in entropy upon melting, compared with the crystal of a less symmetrical molecule. The residual entropy due to molecular symmetry has the direct effect of reducing the entropy gain upon melting (a negative effect). However, molecular symmetry also exerts indirect effects on both the entropy and enthalpy of melting. These indirect effects, imposed by the condition of equilibrium melting, are positive, such that it is the balance between the direct and indirect effects what determines the value observed for the entropy of melting of the symmetric molecules. When the indirect effect of molecular symmetry is greater than its direct effect, the observed entropy gain upon melting of the more symmetrical molecule is greater than that of a less symmetrical one.     

Effect of urea on the behaviour of poly(2-hydroxyethyl methacrylate)-water mixtures

The effect of urea solutions on the equilibrium swelling of lightly crosslinked poly(2-hydroxyethyl methacrylate) (PHEMA) gels and on the viscometric behaviour of PHEMA, for various concentrations of urea and temperatures, has been studied. Urea raises the degree of swelling of gels and the intrinsic viscosity of PHEMA; the temperature coefficient of both quantities is negative. A thermodynamic analysis of the swelling data shows that a change in entropy is the driving force for the increase in swelling at low temperatures, while at higher temperatures (50–80°) a negative change in enthalpy prevails, both corresponding to the transport of PHEMA from the aqueous medium into urea solutions. The entropy and enthalpy of dilution parameters derived from viscometric measurements have negative values, and their absolute values decrease with increasing urea concentration. It has also been found that the PHEMA molecules in urea solutions under the θ-conditions are much more coiled than in an organic θ-solvent. The results are interpreted in terms of the existence of inter- and intramolecular hydrophobic bonds and by the destruction of hydrophobic clusters caused by urea.     

Dispersion polymerization of styrene in alcohol media: Effect of initiator concentration,solvent polarity,and temperature on the rate of polymerization

The effects of three different variables (initiator concentration, polarity of the solvent and reaction temperature) on the rate of dispersion polymerization of styrene in alcohols have been investigated. It was found that the rate of polymerization increases with the initiator (AIBN) concentration at the 0% conversion level and becomes independent of it at higher monomer conversions. More significant was the result that the rate was also found to increase with solvent polarity. This is consistent with thermodynamic equilibrium calculations which account for the partitioning behavior of monomer and solvent in both the solution and the particle phases. The results further suggest the existence of two different kinetic regions: one at low conversions, where the reaction takes place primarily in the solution phase, and one at high conversions, where the reaction takes place primarily in the particle phase. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2907–2915, 1997     

Buffer salt effect on pH in the interior of an anion exchange resin

The internal pH of Q Sepharose Fast Flow anion exchange resin in equilibrium with a bis-tris acetate buffer solution is investigated as a function of buffer salt concentration. Direct evidence of a resin phase pH shift is presented. At low buffer salt concentrations of 20 mM NaCl the resin phase pH is found to be as much as 1.1 pH units greater than that of the buffer phase, approaching to within 0.1 units of the buffer phase at salt concentrations greater than 250 mM. An ideal model with no adjustable parameters based on the Boltzmann distribution and the electroneutrality condition provides excellent agreement with experimental observations. The model assumes that small ions do not bind to the resin fixed charge sites and the agreement between the model predictions and observed resin internal pH suggests that strong electrolytes do not form ion pairs with the resin fixed charge sites.     

p-Chlorophenyldiazonium hexafluorophosphate as a catalyst in the polymerization of tetrahydrofuran and other cyclic ethers

p-Chlorophenyldiazonium hexafluorophosphate is shown to be a convenient and effective catalyst for initiating the polymerization of tetrahydrofuran (TH) and other cyclic ethers. The polymerizations apparently proceed without any significant termination or transfer reactions (i.e., “living” polymers result), and materials of very high molecular weight can be obtained. A mobile monomer-polymer equilibrium for THF was obtained during polymerization and equilibrium conversions were determined at a number of temperatures. The ceiling temperature derived from these data was 84°C., the heat of polymerization was ?4.58 kcal./mole and the corresponding entropy change was ? 17.7 cal./°C.-mole. Hydrocarbons are suitable inert solvents for these polymerizations, but concentrated solutions must be used at ambient temperatures in order to stay above the required equilibrium monomer conceiitration and also to dissolve the catalyst which is insoluble in hydrocarbons. It was shown that acyclic ethers act as transfer agents in these polymerizations and that transfer with consequent reduction of molecular weight continues even after monomer-polymer equilibrium is reached. Cyclic ethers do not act as transfer agents but only copolymerize. Trimethyl orthoformate was shown to be a particularly effective transfer agent; it resulted in a polymer with methoxy endgroups and produced methyl formate as a by-product. The data obtained are consistent with a mechanism involving initiation by hydrogen abstraction and polymerization via tertiary oxonium ions associated with PF^?₆ gegenions. This gegenion is thought to be responsible for the “living” nature of the system.     

Influence of temperature on the adsorption of mellitic acid onto kaolinite

The adsorption of mellitic acid (benzene-1,2,3,4,5,6-hexacarboxylic acid) onto kaolinite was investigated at five temperatures between 10 and 70 degrees C. Mellitic acid adsorption increased with increasing temperature at low pH (below pH 5.5), but at higher pH, the effect of increasing temperature was to reduce the amount adsorbed. Potentiometric titrations were conducted, adsorption isotherms were measured over the same temperature range, and the data obtained were used in conjunction with adsorption edge and ATR-FTIR spectroscopic data to develop an extended constant capacitance surface complexation model of mellitic acid adsorption. A single set of reactions was used to model all data at the five temperatures studied. The model indicates that mellitic acid sorbs via outer-sphere complexation to surface hydroxyl (SOH) groups on the kaolinite surface rather than to permanent charge sites. The reactions proposed are SOH + L6- + 2H+ <-->[(SOH2)+(LH)5-]4- and SOH + L(6-) <--> [(SOH)(L)6-]6-. Thermodynamic parameters calculated from the temperature dependence of the equilibrium constants for these reactions indicate that the adsorption of mellitic acid onto kaolinite is accompanied by a large entropy increase.     

Solution and Mixing Thermodynamics of Propranolol and Atenolol in Aqueous Media

Based on the van’t Hoff and Gibbs equations, the thermodynamic functions Gibbs energy, enthalpy, and entropy of dissolution, and of mixing of propranolol (PPN) and atenolol (ATN) in water at pH=11.5, were evaluated from solubility values determined at several temperatures. The equilibrium solubility values obtained for ATN were almost three hundred-fold higher than those for PPN. The enthalpies of dissolution were positive for both drugs, whereas the entropies of dissolution were both negative indicating a greater molecular organization after the drugs’ dissolution processes. Otherwise, the entropies of mixing were also negative in both cases indicating mixing-entropy is driving on drugs dissolution processes. The results were discussed in terms of solute-solvent interactions, especially hydrophobic hydration.     

Solubility of silybin in aqueous poly(vinylpyrrolidone) solution

Silybin is a main component in silymarin, which is an antihepatotoxic polyphenolic substance isolated from the milk thistle plant, Silybum marianum. A major problem in the development of an oral solid dosage form of this drug is the extremely poor aqueous solubility. In present work, the solubility of silybin in aqueous poly(vinylpyrrolidone) (PVP k30) solution at the temperature range from 293.15 to 313.15 K was measured by a solid–liquid equilibrium method. Experimental results reveal that the solubility of silybin increases with the increase both in PVP's concentration and temperature. With the increase in PVP's concentration, the transfer enthalpy for silybin from water to aqueous PVP solution decreases within a negative region, and the transfer entropy increases slightly first in a positive region and then decreases to a negative region. The transfer enthalpy is lower than the entropy term. A modified UNIQUAC model was used to correlate solubility data.     

Thermodynamic quantities relative to solution processes of Naproxen in aqueous media at pH 1.2 and 7.4

Based on van’t Hoff and Gibbs equations, the thermodynamic functions Gibbs free energy, enthalpy, and entropy of solution, mixing and solvation of naproxen (NAP) in water at pH 1.2 and 7.4, were evaluated from solubility values determined at several temperatures. The solubility at pH 7.4 and 25.0°C was almost 150 times higher with respect to pH 1.2. The enthalpies of solution were positive and greater for pH 1.2, while the entropies of solution were both negative, thereby implying a greater molecular organization at pH 7.4. The results were discussed in terms of solute–solvent interactions.     

Investigating interfacial parameters with platinum single crystal electrodes

The concepts of total and free charge of platinum single crystal electrodes are revised in this paper, together with the associated concepts of potential of zero total and free charge. Total charges can be measured from CO displacement method. Results on solution of different pH are described. A novel buffer composition is used to attain pH values close to neutrality while avoiding interferences from anion adsorption processes. Stress is made on the fact that free charges are not accessible through electrochemical measurement for systems at equilibrium since adsorption processes (hydrogen and hydroxyl) interfere with free charge determination. Still, a model is described that allows, under some assumptions, extract free charge values and the corresponding potential of zero free charge for Pt(111) electrodes. On the other hand, fast measurement outside equilibrium can separate free charges from adsorption processes based on their different time constant. In this way, the laser induced temperature jump experiment allows determination of the potential of maximum entropy, a magnitude that is intimately related with the potential of zero free charge. Values of the potential of maximum entropy as a function of pH are given for the different basal planes of platinum.     

Characterization of the interaction between human plasma fibronectin and collagen by means of affinity electrophoresis.

The interaction between human plasma fibronectin and different types and forms of collagen were analysed by affinity electrophoresis at different pH values. The fibronectin bound tightly to collagen type I, III and IV, but not to type V. The fibronectin interacted better with the denatured form of collagen type I (gelatin) than with the native form. At pH less than 5.5 the fibronectin exhibited much lower affinity to gelatin than at pH greater than 8.0. The interaction between the fibronectin and gelatin was further analysed by affinity electrophoresis in which apparent dissociation constants (Kd) of the fibronectin for gelatin were calculated, and effects of urea, 2-mercaptoethanol and temperature on the interaction were examined. The fibronectin markedly diminished its affinity to gelatin at 3 M urea to give Kd = 2.5 x 10(-6) M, which was 1000 times larger than the value without urea. The fibronectin dissociated into its monomers and the monomers diminished their affinity to gelatin in a stepwise fashion with increase in concentration of 2-mercaptoethanol. The fibronectin diminished the affinity to gelatin by elevating temperature, and van't Hoff plots of log Kd values against the reciprocal of absolute temperature (T) showed that log Kd was inversely proportional to 1/T in the range 15-50 degrees C, and the thermodynamic parameters of the standard enthalpy change, the standard free energy change and the entropy change at 37 degrees C for association of fibronectin and gelatin were all negative. At 60 degrees C the affinity of fibronectin to gelatin was not detectable.(ABSTRACT TRUNCATED AT 250 WORDS)