Effect of substituent on the thermodynamics of D-glucopyranoside binding to concanavalin A, pea (Pisum sativum) lectin and lentil (Lens culinaris) lectin

Titration calorimetry measurements of the binding of phenyl-alpha (alpha PhOGlu), 3-methoxy (3MeOGlu), fluorodeoxy and deoxy derivatives of alpha-D-glucopyranose (Glu) to concanavalin A (conA), pea lectin and lentil lectin were performed at approx. 10 and 25 degrees C in 0.01 M dimethylglutaric acid/NaOH buffer, pH 6.9, containing 0.15 M NaCl and Mn2+ and Ca2+ ions. Apparently the 3-deoxy, 4-deoxy and 6-deoxy as well as the 4-fluorodeoxy and 6-fluorodeoxy derivatives of Glu do not bind to the lectins because no heat release was observed on the addition of aliquots of solutions of these derivatives to the lectin solutions. The binding enthalpies, delta H0b, and entropies, delta S0b, determined from the measurements were compared with the same thermodynamic binding parameters for Glu, D-mannopyranoside and methyl-alpha- D-glucopyranoside (alpha MeOGlu). The binding reactions are enthalpically driven with little change in the heat capacity on binding, and exhibit enthalpy-entropy compensation. Differences between the thermodynamic binding parameters can be rationalized in terms of the interactions apparent in the known crystal structures of the methyl-alpha-D-mannopyranoside-conA [Derewenda, Yariv, Helliwell, Kalb (Gilboa), Dodson, Papiz, Wan and Campbell (1989) EMBO J. 8, 2189-2193] and pea lectin-trimanno-pyranoside [Rini, Hardman, Einspahr, Suddath and Carber (1993) J. Biol. Chem. 268, 10126-10132] complexes. Increases in the entropy change on binding are observed for alpha MeOGlu binding to pea and lentil lectin, for alpha PhOGlu binding to conA and pea lectin, and for 3MeOGlu binding to pea lectin relative to the entropy change for Glu binding, and imply that the phenoxy and methoxy substituents provide additional hydrophobic interactions in the complex. Increases in the binding enthalpy relative to that of Glu are observed for deoxy and fluoro derivatives in the C-1 and C-2 positions and imply that these substituents weaken the interaction with the surrounding water, thereby strengthening the interaction with the binding site.

Studies on a chitooligosaccharide-specific lectin from Coccinia indica. Thermodynamics and kinetics of umbelliferyl glycoside binding.

Coccinia indica agglutinin (CIA) is a chitooligosaccharide-specific lectin with two binding sites/homodimer of M(r) 32,000. Quenching studies implied tryptophan involvement in binding activity, which was confirmed by chemical modification experiments (A. R. Sanadi and A. Surolia, submitted for publication). Binding of 4-methylumbelliferyl chitooligosaccharides has been carried out to study their binding by CIA. Reversal experiments confirm the validity of the data previously obtained (A. R. Sanadi and A. Surolia, submitted for publication) from intrinsic fluorescence studies. Surprisingly, unlike wheat germ agglutinin, there is no consistent thermodynamic effect of the chromophoric label on binding activities as compared with the native sugars. From the changes in the optical properties of the chromophoric group upon binding to CIA, it has been possible to confirm that the tryptophan located in the binding site is closest to the fourth subsite. Thermodynamic analysis shows that the binding of the labeled tetrasaccharide is very strongly entropically driven, with the terminal, nonreducing sugar residue protruding from the binding pocket. The results of stopped-flow kinetic studies on the binding of the chromophoric trisaccharide by CIA show that the mechanism of binding is a one-step process.

Thermodynamics of monosaccharide binding to concanavalin A, pea (Pisum sativum) lectin, and lentil (Lens culinaris) lectin

Titration calorimetry measurements of the binding of methyl alpha-D-mannopyranoside (Me alpha Man), D-mannopyranoside (Man), methyl alpha-D-glucopyranoside (Me alpha Glu), and D-glucopyranoside (Glu) to concanavalin A (Con A), pea lectin, and lentil lectin were performed at 281 and 292 K in 0.01 M dimethylglutaric acid-NaOH buffer (pH 6.9) containing 0.15 M NaCl and Mn+2 and Ca+2 ions. The site binding enthalpies, delta H, are the same at both temperatures and range from -28.4 +/- 0.9 (Me alpha Man) to -16.6 +/- 0.5 kJ mol-1 (Glu) for Con A, from -26.2 +/- 1.1 (Me alpha Man) to -12.8 +/- 0.4 kJ mol-1 (Me alpha Glu) for pea lectin, and from -16.6 +/- 0.7 (Me alpha Man) to -8.0 +/- 0.2 kJ mol-1 (Me alpha Glu) for lentil lectin. The site binding constants range from 17 +/- 1 x 10(3) M-1 (Me alpha Man to Con A at 281.2 K) to 230 +/- 20 M-1 (Glu to lentil lectin at 292.6 K) and exhibit high specificity for Con A where they are in the Me alpha Man:Man:Me alpha Glu:Glu ratio of 21:4:5:1, while the corresponding ratio is 5:2:1.5:1 for pea lectin and 4:2:2:1 for lentil lectin. The higher specificity for Con A indicates more interactions between the amino acid residues at the binding site and the carbohydrate ligand than for the pea and lentil lectin-carbohydrate complexes. The carbohydrate-lectin binding results exhibit enthalpy-entropy compensation in that delta Hb (kJ mol-1) = -1.67 +/- 0.06 x 10(4) + (1.30 +/- 0.12)T(K) delta Sb (J mol-1K-1). Differential scanning calorimetry measurements on the thermal denaturation of the lectins and their carbohydrate complexes show that the Con A tetramer dissociates into monomers, while the pea and lentil lectin dimers dissociate into two submonomer fragments. At the denaturation temperature, one carbohydrate binds to each monomer of Con A and the pea and lentil lectins. Complexation with the carbohydrate increases the denaturation temperature of the lectin and the magnitude of the increases yield binding constants in agreement with the determinations from titration calorimetry.

Thermodynamics of the binding of galactopyranoside derivatives to the basic lectin from winged bean (Psophocarpus tetrogonolobus)

The thermodynamics of the binding of D-galactopyranoside (Gal), 2-acetamido-2-deoxygalactopyranoside (GalNAc), methyl-alpha-D-galactopyranoside, and methyl-beta-D-galactopyranoside to the basic agglutinin from winged bean (WBAI) in 0.02 M sodium phosphate and 0.15 M sodium chloride buffer have been investigated from 298.15 to 333.15 K by titration calorimetry and at the denaturation temperature by differential scanning calorimetry (DSC). WBAI is a dimer with two binding sites. The titration calorimetry yielded single-site binding constants ranging from 0.56 +/- 0.14 x 10(3) M-1 for Gal at 323.15 K to 7.2 +/- 0.5 x 10(3) M-1 for GalNAc at 298.15 K and binding enthalpies ranging from -28.0 +/- 2.0 kJ mol-1 for GalNAc at 298.15 K to -14.3 +/- 0.1 kJ mol-1 for methyl-beta-D-galactopyranoside at 322.65 K. The denaturation transition consisted of two overlapping peaks over the pH range 5.6-7.4. Fits of the differential scanning calorimetry data to a two-state transition model showed that the low temperature transition (341.6 +/- 0.4 K at pH 7.4) consisted of two domains unfolding as a single entity while the higher temperature transition (347.8 +/- 0.6 K at pH 7.4) is of the remaining WBAI dimer unfolding into two monomers. Both transitions shift to higher temperatures and higher calorimetric enthalpies with increase in added ligand concentration at pH 7.4. Analysis of the temperature increase as a function of added ligand concentration suggests that one ligand binds to the two domains unfolding at 341.6 +/- 0.6 K and one ligand binds to the domain unfolding at 347.8 +/- 0.6 K.

Thermodynamics of GdMnO3 and GdMn2O5 phases determined by the EMF method

Using solid oxide galvanic cells of the type: MnO + Gd2O3 + GdMnO3/O-2/Ni + NiO and Mn3O4 + GdMnO3 + GdMn2O5/O-2/air the equilibrium oxygen pressure for the following reactions :MnO + 1/2Gd(2)O(3) + 1/4O(2) = GdMnO3 1/3Mn(3)O(4) + GdMnO3 + 1/3O(2) = GdMn2O5 was determined in the temperature range from 1073 to 1450 K. From the determined equilibrium oxygen partial pressure the corresponding G i b b s free energy change for these reactions was derived: Delta G(f,GdMnO3)(0) (+/- 425J) 132721(+/ - 2240) +51.91(+/ - 0.81)T Delta G(f,GdMn2O5)(0)(+/- 670J) 121858(+/ - 6176) + 79.52(+/ - 4.83)T From these data, standard G i b b s energies, enthalpies and entropies of formation of GdMnO3 and GdMn2O5 from component oxides and from the elements are derived. Thermodynamic data tables for the two ternary phases are compiled from 298.15 to 1400 K.

Thermodynamics of Cobalt (II, III) Oxide (Co3O4): Evidence of Phase Transition

The Gibbs' energy change for the reaction, 3CoO (r.s.)+1/2O2(g)→Co3O4(sp), has been measured between 730 and 1250 K using a solid state galvanic cell: Pt, CuO+Cu2O|(CaO)ZrO2|CoO+Co3O4,Pt. The emf of this cell varies nonlinearly with temperature between 1075 and 1150 K, indicating a second or higher order phase transition in Co3O4around 1120 (±20) K, associated with an entropy change of ∼43 Jmol-1K-1. The phase transition is accompanied by an anomalous increase in lattice parameter and electrical conductivity. The cubic spinel structure is retained during the transition, which is caused by the change in CO+3 ions from low spin to high spin state. The octahedral site preference energy of CO+3 ion in the high spin state has been evaluated as -24.8 kJ mol-1. This is more positive than the value for CO+2 ion (-32.9 kJ mol-1). The cation distribution therefore changes from normal to inverse side during the phase transition. The transformation is unique, coupling spin unpairing in CO+3 ion with cation rearrangement on the spinel lattice, DTA in pure oxygen revealed a small peak corresponding to the transition, which could be differentiated from the large peak due to decomposition. TGA showed that the stoichiometry of oxide is not significantly altered during the transition. The Gibbs' energy of formation of Co3O4 from CoO and O2 below and above phase transition can be represented by the equations:ΔG0=-205,685+170.79T(±200) J mol-1(730-1080 K) and ΔG0=-157,235+127.53T(±200) J mol-1(1150-1250 K).

Thermodynamics Of Aluminum Strontium Alloys

The activity of strontium in liquid Al-Sr alloys (X(Sr) less-than-or-equal-to 0.17) at 1323 K has been determined using the Knudsen effusion-mass loss technique. At higher concentrations (X(Sr) greater-than-or-equal-to 0.28), the activity of strontium has been determined by the pseudoisopiestic technique. Activity of aluminium has been derived by Gibbs-Duhem integration. The concentration - concentration structure factor of Bhatia and Thornton at zero wave vector has been computed from the thermodynamic data. The behaviour of the mean square thermal fluctuation in composition and the thermodynamic mixing functions suggest association tendencies in the liquid state. The associated solution model with Al2Sr as the predominant complex can account for the properties of the liquid alloy. Thermodynamic data for the intermetallic compunds in the Al-Sr system have been derived using the phase diagram and the Gibbs' energy and enthalpy of mixing of liquid alloys. The data indicate the need for redetermination of the phase diagram near the strontium-rich corner.

Thermodynamics of Phosphorus and Sulphur Removal during Basic Oxygen Steelmaking

Removal of impurity elements from hot metal is essential in basic oxygen steelmaking. Oxidation of phosphorus from hot metal has been studied by several authors since the early days of steelmaking. Influence of different parameters on the distribution of phosphorus, seen during the recent work of the authors, differs somewhat from that reported earlier. On the other hand, removal of sulphur during steelmaking has drawn much less attention. This may be due to the magnitude of desulphurisation in oxygen steelmaking being relatively low and desulphurisation during hot metal pre-treatment or in the ladle furnace offering better commercial viability Further, it is normally accepted that sulphur is removed to steelmaking slag in the form of sulphide only However, recent investigations have indicated that a significant amount of sulphur removed during basic oxygen steelmaking can exist in the form of sulphate in the slag under oxidising conditions. The distribution of sulphur during steelmaking becomes more important in the event of carry-over of sulphur-rich blast-furnace slag, which increases sulphur load in the BOF. The chemical nature of sulphur in this slag undergoes a gradual transition from sulphide to sulphate as the oxidative refining progresses.

Resolution of conflicting views on thermodynamics of glass transition: A unified model

Classical description of thermodynamic properties during glass transition has been questioned by the entropy-loss model. The uncompensated loss of entropy at the glass transition temperature and zero residual entropy is at the heart of the controversy. Both the models are critically reviewed. A unified model is presented which incorporates features of both entropy loss and residual entropy. It implies two different types of contributions to the entropy of the supercooled liquid, one of which vanishes at the transition and the other which contributes to residual entropy. Entropy gain during spontaneous relaxation of glass, and the nature of heat capacity `hysteresis' during cooling and heating through the glass transition range support the proposed model. Experiments are outlined for differentiating between the models.

Thermodynamics and phase equilibria in the Ga---Sb system

The optimum values of the solution parameters of a multiparameter integral free-energy function have been determined using experimental data from the Ga-Sb system. The equation is represented as DELTAG(xs) = x(1 - x)[(1 - x)(a1 + a2T + a3T ln T) + x(a4 + a5T + a6T ln T) + x(1 - x)(a7 + a8T + a9xT)].The integral and the corresponding partial form of the free energy function have been found to be of use when interpreting the high temperature thermodynamic data, atomic interactions and phase equilibria in the Ga-Sb system.

Thermodynamics and phase equilibria in the system Ga---In using multi-parameter functions

A four and a five-parameter functions are used to analyse and interpret the high and low temperature thermodynamic data and phase equilibria in the Ga-In system.