Crystal field interactions in DyFe2Si2 and DyFe2Ge2

Two sets of crystal field (CF) parameters have been proposed for DyFe₂Si₂, none of which could provide a simultaneous explanation of the available experimental data, particularly at low temperatures (below 100 K). The set derived from magnetic studies could not even explain the thermal variation of the magnetic specific heat reported in the same work. Although the set of CF parameters, obtained from a fit to the Mossbauer spectra, could provide a fairly good explanation of the thermal variation of the magnetic susceptibilities along the c-axis, it could not explain the observed thermal variation of other reported experimental findings. In the present work, an appraisal of the CF parameters proposed earlier has been done and a set of CF parameters has been derived, which provide a simultaneous explanation of all the available experimental data. The effect of substitution of Ge for Si on the magnetic properties and the magnetic specific heat of DyFe₂Si₂ has been studied in the framework of one electron crystal field model. The inelastic neutron scattering studies and EPR measurements are required to check the predicted Stark energies and the paramagnetic resonance g-values.     

Synthesis,crystal structures and magnetic behaviors of two dicyanamide bridged di- and polynuclear complexes of cobalt(II) derived from 2,4,6-tris(2-pyridyl)1,3,5-triazine and imidazole

Two new dicyanamido-bridged di- and polynuclear complexes of Co(II), [Co(dca)(tptz)(H₂O)]₂·2(ClO₄) (1) and [Co(dca)₂(imz)₂]_n (2) [dca, dicyanamide; tptz, 2,4,6-tris(2-pyridyl)1,3,5-triazine; and imz, imidazole] have been synthesized and characterized structurally, as well as magnetically. The X-ray single crystal structure determination of complex 1 shows that two symmetry related octahedral Co(II) ions are separated by dca ligand and other coordination sites are satisfied by tptz and aquo ligands. Each dinuclear unit is associated with each other by intramolecular hydrogen bonding interactions, giving rise to a 1D chain structure. On the other hand complex 2 is a 1D coordination polymer having [Co(II)(imz)₂] units connected by double bridging dca ligands. These 1D chains interact through face-to-face π–π stacking interactions of the imz rings extending the dimensionality to a 2D supramolecular network. The variable temperature (300–2 K) magnetic measurements of both compounds reveal that dicyanamide exhibits a weak antiferromagnetic interaction between the metal centers.     

Syntheses,Characterization and X‐ray Structure of the First Silver(I) Complexes with 4‐Amino‐3‐thioxo‐3,4‐dihydro‐1,2,4‐triazin‐5(2H)‐one

Reaction of thiocarbohydrazide with glyoxolic acid monohydrate led to 4‐amino‐3‐thioxo‐3,4‐dihydro‐1,2,4‐triazin‐5(2H)‐one (AHTTO, 1 ). Treatment of 1 with AgNO₃ and PPh₃ gave thecomplexes [(PPh₃)₂Ag₂(μ‐N,S‐AHTTO)₂](NO₃)₂ ( 2 ) and [(PPh₃)₂Ag(AHTTO)]NO₃ · MeOH ( 3 ) was obtained under different conditions. All the compounds have been characterized by elemental analyses, IR spectroscopy and X‐ray diffraction studies.     

Fluorimetric study on the charge transfer behavior of trans-ethyl-(p-dimethylamino cinnamate) and its derivative in cyclodextrin cavities

The intramolecular charge transfer (ICT) property of trans-ethyl p-(dimethylamino) cinnamate (EDAC) and its acid derivative, p-(dimethylamino) cinnamic acid (DMACA), is used to monitor the encapsulation behavior of these probes into the cyclodextrin (CD) nanocavities by steady state and picosecond time-resolved fluorescence spectroscopy. The ICT fluorescence band intensity was found to increase with concomitant blue shift in presence of cyclodextrins. The encapsulation behavior was further characterized by increase in emission yield, fluorescence anisotropy as well as lifetime values. Detailed analysis of the spectroscopic data indicate that the probes enter through the dimethyl amino group pointing to the secondary rim of the doughnut-shaped hydrophobic cavities to form 1:1 complex at different pH, however, the extent of penetration is more for EDAC compared with DMACA.     

Fluorescence properties of trans-ethyl-p-(dimethylamino) cinnamate in presence of bile acid host

The knowledge of the formation of bile acid micellar aggregates is of great importance because of the biological significance of these compounds and their pharmacological applications. The intramolecular charge transfer (ICT) fluorescence property of trans-ethyl-p-(dimethylamino) cinnamate is used to study the micelles formed by aggregation of three most important bile acids, viz. cholic acid, deoxycholic acid and chenodeoxycholic acid by steady state and picosecond time-resolved fluorescence spectroscopy. The ICT fluorescence band intensity was found to increase with concomitant blue shift with the addition of bile acids. The blue shift in ICT fluorescence maxima as well as decrease in nonradiative decay constants in presence of bile acids indicate the passage of the probe towards the micro domains formed from the aggregated bile acids. Binding constant of the probe with micelles as well as critical micelle concentration and average polarity parameter of the micellar environments were obtained from the variation of fluorescence intensity on increasing concentration of bile acids in the medium.     

Physicochemical studies on the micellization behavior of cetylpyridinium chloride and triton X-100 binary mixtures in aqueous medium

Physicochemistry of micellization of binary mixtures of cetylpyridinium chloride (CPC) and Triton X-100 (TX-100) have been investigated and the data collected have been analyzed and correlated. Tensiometric, conductometric, spectrophotometric, calorimetric and polarographic methods have been employed in the study. Parameters like critical micellar concentration (CMC), counter-ion binding, energetics of micellization, interfacial surfactant adsorption and minimum area of amphiphile head groups at CMC have been determined. The diffusion coefficients of pure and mixed micelles in solution have been determined by the polarographic method. The regular solution theory of Rubingh has been considered to get information on the micellar composition and their mutual interaction (synergistic for the studied system) in solution. The packing of the monomer in micelle has been estimated to witness spherical geometry for CPC and its mixtures with TX-100, whereas the later has been found to be spheroidal. Polarographic measurements have evidenced comparable diffusion coefficients of CPC and TX-100 micelles whereas their mixed micelles have shown lower values with a minimum, at equimolar composition.     

Exact asymptotics of the characteristic polynomial of the symmetric Pascal matrix

We have obtained the exact asymptotics of the determinant . Inverse symbolic computing methods were used to obtain exact analytical expressions for all terms up to relative order L⁻¹⁴ to the leading term. This determinant is known to give weighted enumerations of cyclically symmetric plane partitions, weighted enumerations of certain families of vicious walkers and it has been conjectured to be proportional to the one point function of the O(1) loop model on a cylinder of circumference L. We apply our result to the loop model and give exact expressions for the asymptotics of the average of the number of loops surrounding a point and the fluctuation in this number. For the related bond percolation model at the critical point, we give exact expressions for the asymptotics of the probability that a point is on a cluster that wraps around a cylinder of even circumference and the probability that a point is on a cluster spanning a cylinder of odd circumference.     

Laguerre minimal surfaces,isotropic geometry and linear elasticity

Laguerre minimal (L-minimal) surfaces are the minimizers of the energy \(\int (H^2-K)/K d\!A\). They are a Laguerre geometric counterpart of Willmore surfaces, the minimizers of \(\int (H^2-K)d\!A\), which are known to be an entity of Möbius sphere geometry. The present paper provides a new and simple approach to L-minimal surfaces by showing that they appear as graphs of biharmonic functions in the isotropic model of Laguerre geometry. Therefore, L-minimal surfaces are equivalent to Airy stress surfaces of linear elasticity. In particular, there is a close relation between L-minimal surfaces of the spherical type, isotropic minimal surfaces (graphs of harmonic functions), and Euclidean minimal surfaces. This relation exhibits connections to geometrical optics. In this paper we also address and illustrate the computation of L-minimal surfaces via thin plate splines and numerical solutions of biharmonic equations. Finally, metric duality in isotropic space is used to derive an isotropic counterpart to L-minimal surfaces and certain Lie transforms of L-minimal surfaces in Euclidean space. The latter surfaces possess an optical interpretation as anticaustics of graph surfaces of biharmonic functions.     

Effect of counterions on the activity of lipase in cationic water-in-oil microemulsions

This paper delineates how the different counterions affect the physicochemical properties of the aqueous aggregates and thereby the lipase activities at the interface of cationic water-in-oil microemulsions. To this end, we have synthesized a series of cetyltrimethylammonium-based surfactants, 1-14, having aliphatic, aliphatic with aromatic substitution at the alpha position, and aromatic carboxylate anion as the counterion. The physicochemical characterizations of these aqueous aggregates were done by conductometric, tensiometric, fluorometric techniques to determine counterion binding (beta), critical micelle concentration (cmc), and micropolarity at the microenvironment. It has been found that the activity of lipase mainly increases with hydrophobicity (which is directly proportional to the counterion binding (beta) of the surfactant) of the counterion and reaches a maximum when the beta value is around 0.5. Increase in hydrophobicity as well as beta leads to the attachment of more counterions at interface resulting in enhancement of interfacial area. Consequently, the enzyme may attain flexible secondary conformation at the augmented surface area and also allow larger population of substrates and enzyme molecules at the interface leading to the enhancement in lipase activity. After an optimum value of beta, further increase probably produces a steric crowding at the interface, hindering the smooth occupancy of enzyme and the substrate in this region leading to decrease of enzyme activity, while molecular surface area of the counterion did not show any virtual influence on the lipase activity. Thus, the variation in the counterion structure and hydrophobicity plays a crucial role in modulating the lipase activity.     

Phase behavior of mixtures of polyoxyethylene(10) stearyl ether (Brij-76), 1-butanol, isooctane, and mixed polar solvents I. Water and formamide (or N,N-dimethyl formamide)

The isothermal phase diagram of the quaternary system polyoxyethylene(10) stearyl ether (Brij-76)/1-butanol/isooctane/water has been constructed at 30 degrees C with equal amounts of oil and water. A regular fishtail diagram was obtained, confirming the establishment of hydrophile-lipophile balance (HLB) in the system. Mixing of formamide (FA) [or N,N-dimethyl formamide (DMF)] with water as a cosolvent altered the HLB and decreased the solubilization capacity of the quaternary system. No three-phase body appeared at high FA or DMF content. Similar observations were noted for temperature-induced phase diagrams. The effect of DMF was more pronounced than that of FA in reducing the maximum solubilization capacity. The results have been summarized on the basis of HLB and mutual solubility of the components.