Titration calorimetric studies to elucidate the specificity of the interactions of polymyxin B with lipopolysaccharides and lipid A

Lipopolysaccharide (LPS), the major cell wall constituent of Gram-negative bacteria, evokes a multitude of biological effects in mammals including pyrogenicity and toxic shock syndrome. Polymyxin B (PmB), a polycationic cyclic peptide, is known to neutralize most of its activities. The nature of the interaction of PmB with LPS and lipid A was investigated by isothermal titration calorimetry. PmB binds to LPS as well as lipid A stoichiometrically and non-co-operatively with micromolar affinity. These interactions are driven primarily by a favourable change in entropy (delta S) and are endothermic in nature. These positive changes in enthalpies decrease with increasing temperature, yielding a heat capacity change, delta Cp, of -2385 J.mol-1.degree-1 for PmB-LPS interactions while the binding of PmB to lipid A displays a delta Cp of -2259 J.mol-1.degree-1. The negative heat capacity changes provide strong evidence for the role of hydrophobic interactions as the driving force for the association of PmB with LPS and lipid A. A correlation of the energetics of these interactions with analyses of the molecular models of PmB suggests that a cluster of solvent-exposed non-polar amino acid side-chains that line one surface of the molecule, together with a ring of positively charged residues on its other surface, are responsible for its strong and stoichiometric binding to LPS.

A bile acid derived potassium ion sensor

A chenodeoxycholic acid based K+ ion sensor has been designed using a modular approach in which a fluorophore and a cation receptor are attached to the bile acid backbone. In the absence of K+ the fluorescence of the molecule is quenched because of through-space, photo-induced electron-transfer from the aza-crown unit. Fluorescence enhancement was observed upon titration with K+ (and other alkali metal ions too). In methanol, good selectivity towards the sensing of K+ has been observed.

Influence of phosphate ligands in abolishing the conformational difference between ribonuclease A and its acid-denatured derivative

The initial structural alteration of RNAase A due to acid denaturation (0.5 N HCl, 30 degrees C) that accompanies deamidation (without altering enzymic activity) has been dectected by spectrophotometric titration, fluorescence and ORD/CD measurements. It is shown that acid treated RNAase A has an altered conformation at neutral pH, 25 degrees C. This is characterized by the increased accessibility of buried tyrosine residue(s) towards the solvent. The most altered conformation of RNAase A is found in the 10 h acid-treated derivative. This has about 1.5 additional exposed tyrosine residues and a lesser amount of secondary structure than RNAase A. All three methods (titration, fluorescence and CD) established that the structural transition of RNAase A is biphasic. The first phase occurs within 1 h and the resulting subtle conformational change is constant up to 7 h. Following this, after the release of 0.55 mol of ammonia, the major conformational change begins. The altered conformation of the acid-denatured RNAase A could be reversed completely to the native state through a conformational change induced by substrate analogs like 2'- or 3'-CMP. Thus the monodeamidated derivative isolated from the acid-denatured RNAase A by phosphate is very similar to RNAase A in over-all conformation. The results suggest the possibility of flexibility in the RNAase A molecule that does not affect its catalytic activity, as probed through the tyrosine residues.

Esterification of stearic acid with p-cresol over modified Indian bentonite clay catalysts

The esterification of stearic acid with p-cresol using modified Indian bentonite clay catalysts has been reported. The reaction was studied over exchanged clays, acid activated clays, exchanged acid activated clays, aluminium pillared clay, aluminium pillared acid activated clay, molecular sieve Al-MCM-41, zeolite H beta, ZrO2, S-ZrO2, p-TSA, montmorillonite K10, and montmorillonite KSF in o-xylene for 6 h. The catalysts were characterized by X-ray diffraction and surface area measurements. The acidity was determined by n-butylamine back-titration method and DRIFTS after pyridine adsorption. Acid activated Indian bentonite (AAIB) was found to be a better catalyst compared to other catalysts in the esterification of stearic acid with p-cresol.

On the acid-base stability of Keggin Al-13 and Al-30 polymers in polyaluminum coagulants

The acid-base stabilities of Al-13 and Al-30 in polyaluminum coagulants during aging and after dosing into water were studied systematically using batch and flow-through acid-base titration experiments. The acid decomposition rates of both Al-13 and Al-30 increase rapidly with the decrease in solution pH. The acid decompositions of Al-13 and Al-30 with respect to H+ concentration are composed of two parallel first-order and second-order reactions, and the reaction orders are 1.169 and 1.005, respectively. The acid decomposition rates of Al-13 and Al-30 increase slightly when the temperature increases from 20 to ca. 35 A degrees C, but decrease when the temperature increases further. Al-30 is more stable than Al-13 in acidic solution, and the stability difference increases as the pH decreases. Al-30 is more possible to become the dominant species in polyaluminum coagulants than Al-13. The acid catalyzed decomposition and followed by recrystallization to form bayerite is one of the main processes that are responsible for the decrease of Al-13 and Al-30 in polyaluminum coagulants during storage. The deprotonation and polymerization of Al-13 and Al-30 depend on solution pH. The hydrolysis products are positively charged, and consist mainly of repeated Al-13 and Al-30 units rather than amorphous Al(OH)(3) precipitates. Al-30 is less stable than Al-13 upon alkaline hydrolysis. Al-13 is stable at pH < 5.9, while Al-30 lose one proton at the pH 4.6-5.75. Al-13 and Al-30 lose respective 5 and 10 protons and form [Al-13] (n) and [Al-30] (n) clusters within the pH region of 5.9-6.25 and 5.75-6.65, respectively. This indicates that Al-30 is easier to aggregate than Al-13 at the acidic side, but [Al-13] (n) is much easier to convert to Alsol-gel than [Al-30] (n) . Al-30 possesses better characteristics than Al-13 when used as coagulant because the hydrolysis products of Al-30 possess higher charges than that of Al-13, and [Al-30] (n) clusters exist within a wider pH range.

Determination of Point of Zero Charge of Tunisian Kaolinites by Potentiometric and Mass Titration Methods

This paper deals with determining points of zero charge of natural and Na+-saturated mineral kaolinites using two methods: (1) acid-base potentiometric titration was employed to obtain the adsorption of H+ and OH- on amphoteric surfaces in solutions of varying ionic strengths in order to determinate graphically the point of zero net proton charge (PZNPC) defined equally as point of zero salt effect (PZSE); (2) mass titration curve at different electrolyte concentrations in order to estimate PZNPCs by interpolation and to compare with those determined by potentiometric titrations. The two methods involved points of zero charge approximately similar for the two kaolinites between 6.5-7.8, comparable to those reported previously and were in the range expected for these clay minerals. The comparison of potentiometric surface titration curves obtained at 25 °C and those published in the literature reveals significant discrepancies both in the shape and in the pH of PZNPCs values.

Formation equilibria of ternary metal complexes with citric acid and glutamine (alanine) in aqueous solution

The species and their formation constants in the ternary, systems were obtained by the Scogs2 software from potentiometric titration data. The Comics software was used to calculate the distribution of species in the ternary systems. MLXH, MLXH2 and MLXH3 are the common species in these systems. The coordination behaviors of the rare earths are very similar and their stability is closely matched. The ternary rare earth complexes are more stable than the corresponding ternary complexes of calcium. The ternary zinc complex with glutamine as the secondary ligand is more stable than the corresponding complexes of rare earths, but the ternary complex with alanine as the secondary ligand shows an inverse trend. The distributions of species in the ternary systems vary with pH changing. A prediction can be made that exogenous rare earths can affect the species of Ca and Zn in human body.

Solvent extraction of scandium(III), yttrium(III), lanthanides(III), and divalent metal ions with sec-nonylphenoxy acetic acid

Such physicochemical properties of sec-nonylphenoxy acetic acid (CA-100) as the solubility in water, acid dissociation constant in water, dimerization constant in heptane, and distribution constant in organic solvent-water were measured by two-phase titration. The extraction behaviors of scandium (III), yttrium (III), lanthanides (III), and divalent metal ions from hydrochloric acid solutions with CA-100 in heptane have been investigated, and the possibilities of separating scandium (yttrium) from lanthanides and divalent metal ions have been carefully discussed. The stoichiometries of the extracted metal complexes were investigated by the slope-analysis technique. The effect of the nature of diluent on the extraction of yttrium (III) with CA100 has been studied and correlated with the dielectric constant.

Determination of surface pK(a) of HS(CH2)(10)COOH SAMs using an electrochemical titration method

The self-assembled monolayer(SAM) of 11-mercaptoundecanoic acid [HS(CH2)(10)COOH] was formed on a gold electrode and the effect of the charge of end group on the electrochemical response of Fe(CN)(6)(3-) at the SAM modified electrode was studied by cyclic voltammetry. At high pH, when the -COOH groups are dissociated, the current of Fe(CN)(6)(3-) is suppressed; as the solution pH is lowered, the current of Fe(CN)(6)(3-) increases. The electrochemical titration curve was obtained by correlating the currents of Fe(CN)(6)(3-) to the different pH values of electrolyte, from which the surface pK(a) was obtained to be 3. 0+/-0. 2. Furthermore, the reason of small pK(a) value was explained using SAMs of different surface coverage.

Determination of some basic constants of sec-octylphenoxy acetic acid

In this work some basic constants of extractant Sec-Octylphenoxy acetic acid (CA-12) such as solubility (S) in water, dissociation constant (K-a) in aqueous solution, dimerization constant( K-2) and distribution constant (K-d) between water and haptane have been determined by two phase titration method. The results are as follows: S = 1.40 x 10(-4) mol/L, K-a = 3.02 x 10(-4), K-2 = 3.56 x 10(2), K-d = 4.06 x 10(2) (25 +/-0.5 degreesC).

Species of rare earth(III) and calcium(II) in the presence of L-aspartic acid and L-arginine

Rare earth (III)-Asp-Arg and Ca(II)-Asp-Arg systems were studied by potentiometric titration under physiological conditon. The species of each system were determined. The distribution of Tb (III) and Ca(II) species was discussed, as well as in the quaternary system of Tb(III)-Ca(II)-Asp-Arg.

Determination of surface pK(a) of SAM using an electrochemical titration method

A self-assembled monolayer (SAM) of 3-mercaptopropionic acid (HSCH2CH2COOH) was formed on a gold electrode. The effect of the charge of the end group on the electrochemical response of Fe(CN)(6)(3-) at the SAM modified electrode was studied by using cyclic voltammetry. At high pH, when the -COOH groups are dissociated, Fe(CN)(6)(3-) current is suppressed; as the solution pH is lowered, Fe(CN)(6)(3-) current increases. The electrochemical titration curve was obtained by correlating the currents to the different electrolyte pH values, from which the surface pK(a) was obtained to be 5.2+/-0.1. Furthermore, a calculation equation was presented to simulate the electrochemical titration. As comparison, the surface pK(a) was also measured by contact angle titration as 5.6+/-0.1. The surface pK(a) values determined by the two methods in our work are consistent and accurate.

NMR titration and molecular model MOPAC calculation of protonation processes of two MRI ligands

The protonation process of two DTPA bis(amide) derivatives, DTPA-BDMA and DTPA-BDEA, was studied by using H-1 NMR titration and MOPAC calculation. Their protonation process was proposed in the order of the central amine, the terminal amines, the central carboxyl, the terminal carboxyl, the other terminal carboxyl and central amine. During the protonation of the terminal amine, there existed a large fraction of proton transfer from the central amine to the other terminal amine.

Tb(111) and Ca(11) ion equilibria in the presence of glutamic acid and glutamine

Tb(111) and Ca(11) ion equilibria in the Presence of glutamic acid and glutamine were studied by potentiometric titration at 37 degrees C and an ionic strength of 0.15mol/L(NaCl). The stability constants for Tb(111) and Ca(11) complexes in the systems were obtained. The species and their distribution in the systems were discussed.