Thermodynamic properties of SmFeO3(S) and SM3R5O12(S)

The enthalpy increments and the standard molar Gibbs energy (G) of formation of SmFeO3(S) and SM3Fe5O12(s) have been measured using a Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. A X-type transition, related to magnetic order-disorder transformation (antiferromagnetic to paramagnetic), is apparent from the heat capacity data at similar to673 K for SmFeO3(s) and at similar to560 K for Sm3Fe5O12(S). Enthalpy increment data for SmFeO3(s) and SM3Fe5O12(s), except in the vicinity of X-transition, can be represented by the following polynomial expressions: {H-m(0)(T) - H-m(0)(298.15 K){/J mol-(1)(+/-1.2%) = -54 532.8 + 147.4 . (T/K) + 1.2 . 10(-4) . (T/K)(2) +3.154 . 10(6) . (T/K)(-1); (298.15 less than or equal to T/K less than or equal to 1000) for SmFeO3(s), and {H-m(0)(T) - H-m(0)(298.15 K)}/J mol(-1) (+/-1.4%) = -192 763 + 554.7 . (T/K) + 2.0 . 10(-6) . (T/K)(2) + 8.161 . 10(6) - (T/K)(-1); (298.15 less than or equal to T/K less than or equal to 1000) for Sm3Fe5O12(s). The reversible emf of the solid-state electrochemical cells, (-)Pt/{SmFeO3(s) + Sm2O3(S) + Fe(s)) // YDT / CSZ // {Fe(s) + Fe0.95O(s)} / Pt(+) and (-)Pt/{Fe(s) + Fe0.95O(S)} // CSZ // {SmFeO3(s) + Sm3Fe5O12(s) + Fe3O4(s) / Pt(+), were measured in the temperature ranges of 1005-1259 K and 1030-1252 K, respectively. The standard molar G of formation of solid SmFeO3 and Sm3Fe5O12 calculated by the least squares regression analysis of the data obtained in the current study, and data for Fe0.95O and Sm2O3 from the literature, are given by: Delta(f)G(m)(0)(SmFeO3, s)/kj . mol(-1)(+/-2.0) = -1355.2 + 0.2643 . ; (1005 less than or equal to T/K less than or equal to 1570) and Delta(f)G(m)(0)(Sm3Fe5O12, s)/kj . mol(-1) (+/- 3.1) = -4891.0 + 1.0312 . (T/K); (1030 less than or equal to T/K less than or equal to 1252) The uncertainty estimates for Delta(f)G(m)(0) include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on these thermodynamic data, the oxygen potential diagram for the system Sm-Fe-O was constructed at 1250 K.

Synergy between the N-terminal and C-terminal domains of Mycobacterium tuberculosis HupB is essential for high-affinity binding, DNA supercoiling and inhibition of RecA-promoted strand exchange

The occurrence of DNA architectural proteins containing two functional domains derived from two different architectural proteins is an interesting emerging research theme in the field of nucleoid structure and function. Mycobacterium tuberculosis HupB, unlike Escherichia coli HU, is a two-domain protein that, in the N-terminal region, shows broad sequence homology with bacterial HU. The long C-terminal extension, on the other hand, contains seven PAKK/KAAK motifs, which are characteristic of the histone H1/H5 family of proteins. In this article, we describe several aspects of HupB function, in comparison with its truncated derivatives lacking either the C-terminus or N-terminus. We found that HupB binds a variety of DNA repair and replication intermediates with K(d) values in the nanomolar range. By contrast, the N-terminal fragment of M. tuberculosis HupB (HupB(MtbN)) showed diminished DNA-binding activity, with K(d) values in the micromolar range, and the C-terminal domain was completely devoid of DNA-binding activity. Unlike HupB(MtbN), HupB was able to constrain DNA in negative supercoils and introduce negative superhelical turns into relaxed DNA. Similarly, HupB exerted a robust inhibitory effect on DNA strand exchange promoted by cognate and noncognate RecA proteins, whereas HupB(MtbN), even at a 50-fold molar excess, had no inhibitory effect. Considered together, these results suggest that synergy between the N-terminal and C-terminal domains of HupB is essential for its DNA-binding ability, and to modulate the topological features of DNA, which has implications for processes such as DNA compaction, gene regulation, homologous recombination, and DNA repair.

Thermodynamic study of oxygen in liquid lead tin alloys

The activity coefficients of oxygen in liquid lead-tin alloys have been measured between 550 and 1100°C by use of solid oxide galvanic cells Pt, Ni-NiO I Zr02 Solid electrolyte I 0 (Pb + Sn), Cermet, Pt Pt, Fe-FeO I Zr02 Solid electrolyte I O(Pb + Sn), Cermet, Pt Alcock and Richardson's quasi-chemical equation, with the coordination number of atoms set to 2, is found to predict successfully the activity coefficients of oxygen in these alloys.The relative partial molar enthalpy and entropy of oxygen ?t 1 atom per cent in the alloys have been calculated from ttva variation of the activity coefficient with temperature. The addition of tin to an unsaturated solution of oxygen in lead is shown to decrease significantly both the partial molar enthalpy and entropy of oxygen. As the measurements were restricted to a narrow range between 750-1100'C in lead-rich alloys, however, the pronounced variation of the partial molar enthalpy of oxygen with temperature at constant alloy composition predicted by the quasi-chemical model could not be verified.

Activities of oxygen and lead in Pb-Ag O solutions

The reversible e.m.f. of galvanic cells: stainlesssteel,Ir,Pb+PbO|CaO+ZrO2|Ag+Pb+PbO,Ir,stainlesssteel,I and Pt,Ni+NiO|CaO+ZrO2|O(Pb+Ag),Cermet,Pt,II incorporating solid oxide electrolytes were measured as a function of alloy composition. In lead-rich alloys, the temperature dependence of the e.m.f. of cell I was also investigated. Since the solubility of oxygen in the alloy is small, the relative partial molar properties of lead in the binary Ag + Pb system can be calculated from the e.m.f. of this cell. The Gibbs free energies obtained in this study are combined with selected calorimetric data to provide a complete thermodynamic discription of liquid Ag + Pb Alloys. The activity coefficient of oxygen in the whole range of Ag + Pb alloys at 1273 K have been obtained from the e.m.f. of cell II; and these are found to deviate positively from Alcock and Richardson's quasichemical equation when the average co-ordination number of all the atoms is assigned a value of 2.

Prediction of activities of oxygen in dilute quaternary solutions using binary data

Equations are developed for predicting the activity coefficients of oxygen dissolved in ternary liquid alloys. These are extensions of earlier treatments, and are based on a model in which each oxygen atom is assumed to make four bonds with neighboring metal atoms. It is also postulated that the strong oxygen-metal bonds distort the electronic configuration around the metal atoms bonded to oxygen, and that the quantitative reduction of the strength of bonds made by these atoms with all of the adjacent metal atoms is equivalent to a factor of approximately two. The predictions of the quasichemical equation which is derived agree satisfactorily with the partial molar free energies of oxygen in Ag-Cu-Sn solutions at 1200°C reported in literature. An extension of this treatment to multicomponent solutions is also indicated.

Solubilities of Pb+2, Bi+3, Sb+3 and Cu+1 sulphides in (NaCl KCl Na2S) melts

Solubilities of common metal sulfides have been determined in the (NaCl+KCl) eutectic melt with and without Na2S. A novel gas-phase equilibrium technique has been used for PbS, Bi2S3, and So2S3, and an improved liquid phase equilibrium technique for Cu2S, which eliminates the errors due to physical entrapment of the sulfide phase and segregation on quenching, enabling precise measurements to be made. Solubilities in the (NaCl+KCl) eutectic melt were determined as a function of temperature in the rante 700° to 950°C, and were found to be small. The partial molar heats of mixing of the sulfides in the eutectic melt have been calculated from the solubility measurements, to be 13.3, 31.4, 37.1, and 49.0 kcal for PbSs), Sb2S2(l), and Cu2S(s), respectively. Sodium sulfide addition was observed to enhance these solubilities, the effect being largest for Cu2S followed by Sb2S3, Bi2S3, and PbS. This effect is explained qualitatively. It was observed that PbS and Sb2S3 obey Henry's law up to saturation in (NaCl+KCl+Na2S) melts.

An entropy meter based on the thermoelectric potential of a nonisothermal solid electrolyte cell

The theory, design, and performance of a solid electrolyte twin thermocell for the direct determination of the partial molar entropy of oxygen in a single-phase or multiphase mixture are described. The difference between the Seebeck coefficients of the concentric thermocells is directly related to the difference in the partial molar entropy of oxygen in the electrodes of each thermocell. The measured potentials are sensitive to small deviations from equilibrium at the electrodes. Small electric disturbances caused by simultaneous potential measurements or oxygen fluxes caused by large oxygen potential gradients between the electrodes also disturb the thermoelectric potential. An accuracy of ±0.5 calth K−1 mol−1 has been obtained by this method for the entropies of formation of NiO and NiAl2O4. This “entropy meter” may be used for the measurement of the entropies of formation of simple or complex oxides with significant residual contributions which cannot be detected by heat-capacity measurements.

A comparison of the structure of liquid alloys derived from thermodynamic and diffraction studies

A significant amount of research on the thermodynamic properties of molten alloys is undertaken for obtaining insights into their structure . The partial and integral molar enthalpies, entropies and volumes of mixing provide some general information on the nature and strength of atomic bonds and the distribution of atoms. However, until recently it has been difficult to derive specific quantitative information because the excess entropy of mixing contains configurational , vibrational , electronic , and sometimes magnetic contributions which cannot be easily separated.

Thermodynamic properties of Pt5La, Pt5Ce, Pt5Pr, Pt5Tb and Pt5Tm intermetallics

The Gibbs’ energies of formation of Pt5La, Pt5Ce, Pt5Pr, Pt5Tb and Pt5 Tm intermetallic compounds have been determined in the temperature range 870–1100 K using the solid state cell:Ta,M + MF3 /CaF2 /Pt5 M + Pt + MF3 ,TaTaM+MF3CaF2Pt5M+Pt+MF3Ta.The reversible emf of the cell is directly related to the Gibbs’ energy of formation of the Pt5M compound. The results can be summarized by the equations:DGf° á Pt5 La ñ = - 373,150 + 6 ·60 T( ±300 )J mol - 1 DGf° á Pt5 Ce ñ = - 367,070 + 5 ·79 T( ±300 )J mol - 1 DGf° á Pt5 Pr ñ = - 370,540 + 4 ·69 T( ±300 )J mol - 1 DGf° á Pt5 Tb ñ = - 372,280 + 4 ·11 T( ±300 )J mol - 1 DGf° á Pt5 Tm ñ = - 368,230 + 4 ·89 T( ±300 )J mol - 1 Unknown control sequence '\hfill'relative to the low temperature allotropic form of the lanthanide element and solid platinum as standard states The enthalpies of formation of all the Pt5M intermetallic compounds obtained in this study are in good agreement with Miedema’s model. The experimental values are more negative than those calculated using the model. The variation of the thermodynamic properties of Pt5M compounds with atomic number of the lanthanide element is discussed in relation to valence state and molar volume.

Signature of a silver phase percolation threshold in microscopically phase separated ternary Ge0.15Se0.85-xAgx (0≤x≤0.20) glasses

Temperature modulated alternating differential scanning calorimetric studies show that Se rich Ge0.15Se0.85−xAgx (0 x 0.20) glasses are microscopically phase separated, containing Ag2Se phases embedded in a Ge0.15Se0.85 backbone. With increasing silver concentration, Ag2Se phase percolates in the Ge–Se matrix, with a well-defined percolation threshold at x = 0.10. A signature of this percolation transition is shown up in the thermal behavior, as the appearance of two exothermic crystallization peaks. Density, molar volume, and microhardness measurements, undertaken in the present study, also strongly support this view of percolation transition. The superionic conduction observed earlier in these glasses at higher silver proportions is likely to be connected with the silver phase percolation.

Optical diffraction of second-harmonic signals in the LiBO2-Nb2O5 glasses induced by self-organized LiNbO3 crystallites

The nanocrystallites ( ≈ 3 nm) of LiNbO3, evolved in the (100−x)LiBO2-xNb2O5 (5x20, in molar ratio) glass system exhibited intense second-harmonic signals in transmission mode when exposed to infrared (IR) light at λ = 1064 nm. The second-harmonic waves were found to undergo optical diffraction which was attributed to the presence of self-organized submicrometer-sized LiNbO3 crystallites that were grown within the glass matrix along the parallel damage fringes created by the IR laser radiation. Micro-Raman studies carried out on the laser-irradiated samples confirmed the self-organized crystallites to be LiNbO3.

Photo-induced DNA cleavage activity and remarkable photocytotoxicity of lanthanide(III) complexes of a polypyridyl ligand

Lanthanide(III) complexes [Ln(pyphen)(acac)(2)(NO3)] (1, 2), [Ln(pydppz)(acac)(2)(NO3)] (3, 4) and [La(pydppz)(anacac)(2)(NO3)] (5), where Ln is La(III) (in 1, 3, 5) and Gd(III) (in 2, 4), pyphen is 6-(2-pyridyl)-1,10-phenanthroline, pydppz is 6-(2-pyridyl)-dipyrido[3,2-a:2',3'-c] phenazine, anacac is anthracenylacetylacetonate and acac is acetylacetonate, were prepared, characterized and their DNA photocleavage activity and photocytotoxicity studied. The crystal structure of complex 2 displays a GdO6N3 coordination. The pydppz complexes 3-5 show an electronic spectral band at similar to 390 nm in DMF. The La(III) complexes are diamagnetic, while the Gd(III) complexes are paramagnetic with seven unpaired electrons. The molar conductivity data suggest 1 : 1 electrolytic nature of the complexes in aqueous DMF. They are avid binders to calf thymus DNA giving K-b in the range of 5.4 10(4)-1.2 x 10(6) M-1. Complexes 3-5 efficiently cleave supercoiled DNA to its nicked circular form in UV-A light of 365 nm via formation of singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) species. Complexes 3-5 also exhibit significant photocytotoxic effect in HeLa cancer cells giving respective IC50 value of 0.16(+/- 0.01), 0.15(+/- 0.01) and 0.26 +/-(0.02) mu M in UV-A light of 365 nm, while they are less toxic in dark with an IC50 value of >3 mu M. The presence of an additional pyridyl group makes the pydppz complexes more photocytotoxic than their dppz analogues. FACS analysis of the HeLa cells treated with complex 4 shows apoptosis as the major pathway of cell death. Nuclear localization of complex 5 having an anthracenyl moiety as a fluorophore is evidenced from the confocal microscopic studies.

Deviation from 3-D Ising critical behaviour in aqueous electrolyte solutions

The near-critical behaviour in complex fluids, comprising electrolyte solutions, polymer solutions and amphiphilic systems, reveals a marked departure from the 3-D Ising behaviour. This departure manifests itself either in terms of a crossover from Ising to mean-field (or classical) critical behaviour, when moving away from a given critical point (Tc), or by the persistence of only mean-field region in the surprisingly close vicinity of Tc. The ilo,non-Ising features of the osmotic compressibility (chi(T,p)) in solutions of electrolytes, that exhibit orle or many liquid-liquid transitions, will be presented. The underlying cause of the breakdown of the anticipated 3-D Ising behaviour in aqueous electrolyte solutions is traced to the structuring induced by the electrolytes. New evidence constituting, measurements of small-angle X-ray scattering (SAXS) and the excess molar volume, is advanced to support the thesis of the close relationship, between the structuring and the deviation from the 3-D Ising critical behaviour in aqueous electrolyte solutions.

Self-assembly of Ru-4 and Ru-8 assemblies by coordination using organometallic Ru(II)(2) precursors: Synthesis, characterization and properties

Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II) complexes [Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) or [Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)(MeOH)(2)(eta(6)-p-cymene)(2)]( O3SCF3)(2) (1b) separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4-benzoquinonato (dhbq) bridged binuclear complex [Ru-2(mu-eta(C6H2O4)-C-4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1c) in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the self-assembled macrocycles 2a-2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear (H-1, C-13 and F-19) NMR, infrared (IR) and electrospray ionization mass spectrometry (ESIMS). In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 angstrom x 12.39 angstrom. Furthermore, the photo-and electrochemical properties of these newly synthesized assemblies have been studied by using UV-vis absorption and cyclic voltammetry analysis.

Waring and Riedel Functions for the Liquid-Vapor Coexistence Curve

There exists a minimum in the Waring function, psi(T) = -d(ln p)/d(1/T), and in the Riedel function, alpha(T) = d(ln p)/d(In T), in the liquid-vapor coexistence curve for most fluids. By analyzing National Institute of Standards and Technology data for the molar enthalpy of vaporization and the compressibility variation at the liquid-vapor phase change of 105 fluids, we find that the temperatures of these minima are linearly correlated with the critical temperature, T-c. Using reduced coordinates, we also demonstrate that the minima are well-correlated with the acentric factor. These correlations are used for testing four well-known vapor pressure equations in the Pitzer corresponding states scheme.