Comparison of Spectroscopic and Lasing Properties of Different Types of Sol-Gel Glass Matrices Containing Rh-6G

Rhodamine-6G (Rh-6G) is embedded in sol-gel glass samples which have been prepared by three different methods namely: 1) using HCl as catalyst and glycerol as Drying Control Chemical Additive (DCCA), 2) using HCl as catalyst at 60 °C and drying at room temperature and 3) using HCl as catalyst at 60 °C and heated at 600 °C for 3 h. Comparative studies of spectroscopic and lasing properties of the three types of Rh-6G containing samples were carried out with the lapse of time upto 8 months. Photostability of Rh-6G containing sol-gel samples is measured in terms of half life under Nitrogen laser pumping as number of pulses of N₂ laser necessary to reduce the dye laser intensity to 50% of the original value and value is 7500 pulses at 1.67 Hz rate. The best performance of Rh-6G, as far as its spectroscopic and lasing properties are concerned was found in third type of host matrices using HCl as catalyst at 60 °C and heated at 600 °C for 3 h.     

Computer modeling of MWIR single heterojunction photodetector based on mercury cadmium telluride

In the present paper, an abrupt heterojunction photodetector based on Hg_1 − xCd_xTe (MCT) has been simulated theoretically for mid-infrared applications. A semi-analytical simulation of the device has been carried out in order to study the performance ratings of the photodetector for operation at room temperature. The energy band diagram, carrier concentration, electric field profile, dark current, resistance–area product, quantum efficiency and detectivity have been calculated and optimized as a function of different parameters such as device thickness, applied reverse voltage and operating wavelength. The effect of energy band offsets in conduction and valance band on the transportation of minority carriers has been studied. The influences of doping concentration, electron affinity gradient and the p–n junction position within heterostructure on potential barrier have been analyzed. The optical characterization has been carried out in respect of quantum efficiency, and detectivity of the heterojunction photodetector. In present model the Johnson–Nyquist and shot noise has been considered in calculation of detectivity. The simulated results has been compared and contrasted with the available experimental results. Results of our analytical-cum-simulation study reveal that under suitable biasing condition, the photodetector offers a dark current, I_D ≈ 6.5 × 10⁻¹² A, a zero-bias resistance–area product, R₀A ≈ 11.3 Ω m², quantum efficiency, η ≈ 78%, NEP = 2 × 10⁻¹² W Hz^1/2 and detectivity D^* ≈ 4.7 × 10¹⁰ mHz^1/2/W.     

General derivation of the total electromagnetic cross sections for an arbitrary particle

This work concerns a common problem in electromagnetic scattering; calculation of the total scattering, extinction, and absorption cross sections for an arbitrary particle. Typical expressions for the cross sections are obtained in terms of the vector spherical wave function expansions for the incident and scattered waves. The unique aspect of this work is that the derivation is carried out specifically without use of the far-field zone approximation. The resulting expressions, valid at any distance, exactly match those obtained from the far-field approximation. This demonstrates that the cross sections are independent of the distance from the particle at which they are calculated as one would expect from energy conservation. Numerical simulations of the near and far-field zone energy flows due to a spherical particle are presented to illustrate several implications of this result.     

Effects of various competing ligands on the kinetics of trace metal complexes of Laurentian Fulvic Acid in model solutions and natural waters

The objective of this work was to study the effects of the following Ligands: Chelex-100, Dowex MAC-3 and Dowex 50WX-8 using Competing Ligand Exchange Method. This objective was achieved by investigating complex dissociation kinetics of trace metals: Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Mn(II) and Pb(II) of a well-characterized Laurentian Fulvic Acid (LFA) in model solutions and in a natural waters of Lake Heva (Québec, Canada). The effects of variation in the competing ligands (including their quantities) on the complex dissociation kinetics were quantitatively characterized by their first-order dissociation rate coefficients. The kinetic lability of the metal complexes varied with the metal-to-LFA ratio, as expected from the theory of metal complexes of the chemically and physically heterogeneous complexants, LFA. The general trend in the metal-binding by the above competing ligands was: Dowex 50WX-8 > Chelex-100 > Dowex MAC-3. However, no difference was found between the Dowex 50WX-8 and Chelex-100 for Cd(II), Zn(II), and Co(II). The results revealed the importance of the quantity of Chelex-100 as a competing ligand in the metal(II)-LFA complexation, on the dissociation kinetics of these complexes in model solutions. By developing Competing Ligand Exchange Method as an analytical technique, for studying the relative affinities of the above competing ligands for metals complexation in natural waters this work has made a substantial contribution to analytical chemistry.     

System Zn–Rh–O: heat capacity and Gibbs free energy of formation using differential scanning calorimeter and electrochemical cell

The standard molar Gibbs free energy of formation of ZnRh₂O₄(s) has been determined using an oxide solid-state electrochemical cell wherein calcia-stabilized zirconia (CSZ) was used as an electrolyte. The oxide cell can be represented by: . The electromotive force was measured in the temperature range from 943.9 to 1,114.2 K. The standard molar Gibbs energy of formation of ZnRh₂O₄(s) from elements in their standard state using the oxide electrochemical cell has been calculated and can be represented by: . Standard molar heat capacity C ^o _p,m(T) of ZnRh₂O₄(s) was measured using a heat flux-type differential scanning calorimeter in two different temperature ranges, from 127 to 299 and 307 to 845 K. The heat capacity in the higher temperature range was fitted into a polynomial expression and can be represented by: . The heat capacity of ZnRh₂O₄(s), was used along with the data obtained from the oxide electrochemical cell to calculate the standard enthalpy and entropy of formation of the compound at 298.15 K.     

Spectral and X-ray Diffraction Studies of <Emphasis Type="Italic">N</Emphasis>-(2-Nitrophenyl)-5-Phenyl-1,3,4-Oxadiazole-2-Amine

Abstract  

Thiosemicarbazides and their derivatives are well known for their use in biological activity and many applications in pharmaceutical and industrial fields. The cyclization of 1-benzoyl-4-(2-nitrophenyl)-3-thiosemicarbazide (BNPTSC) in dimethylformamide (DMF) medium furnished N-(2-nitrophenyl)-5-phenyl-1,3,4-oxadiazole-2-amine (NPPOA). The chemical structure of the above substituted 1,3,4-oxadiazole has been assigned by IR, mass and X-ray diffraction studies. The XRD studies reveal the presence of four types of hydrogen bonds (N–H···O, N–H···N, C–H···O, C–H···N) in the crystal packing. The crystal system was found to be orthorhombic with a space group Pca2(1) and the unit cell dimensions are: a = 26.873(3) ?, b = 6.0827(7) ?, c = 7.8502(10) ?, α = 90°, β = 90°, γ = 90° and Z = 4.     

Use of laterite for the removal of fluoride from contaminated drinking water

The effects of different operational variables on the mechanistic function of laterite in removal of fluoride have been investigated. Thermodynamic parameters such as free energy change, enthalpy, and entropy of the process, as well as the sorption isotherm, were evaluated. The extent of solute removal is determined by initial solute concentration, operational conditions, laterite dose, and solution pH. For a fixed set of experimental conditions, a model equation is developed from which the percent removal corresponding to each load of fluoride is determined. The mechanism of fluoride adsorption is governed by the zero point charge of laterite and follows a first-order rate equation. pH has a vital role influencing the surface characteristics of laterite. To simulate the flow dynamics, fluoride solution was run through a fixed bed column. The pattern of breakthrough curves for different influent fluoride concentration, pH, and column bed height was characterized. The column efficiency was tested from the bed depth-service time model. The elution of the retained fluoride was studied and the effectiveness of column operation was determined by the retention-elution cycles.     

Rate processes with dynamical disorder: a direct variational approach

Using path integral approach, we develop variational approximations to the calculation of survival probability for rate processes with dynamical disorder. We derive both upper and lower bounds to the survival probability using Jensen's inequality. The inequalities involve the use of a trial action for which the path integrals can be evaluated exactly. Any parameter in the trial action can be varied to optimize the bounds. We have also derived a lower bound to the rate of the process. As a simple illustration, we apply the method to the problem of a particle undergoing Brownian motion in a harmonic potential well, in the presence of a delta function sink, for which one can calculate the exact survival probability numerically. The calculation confirms the two inequalities. The method should be very useful in similar but more complex problems where even numerical solution is not possible.     

Conformally flat collapsing stars in <Emphasis Type="Italic">f</Emphasis>(<Emphasis Type="Italic">R</Emphasis>) gravity

The present work includes an analytical investigation of a collapsing spherical star in f(R) gravity. The interior of the collapsing star admits a conformal flatness. Information regarding the fate of the collapse is extracted from the matching conditions of the extrinsic curvature and the Ricci curvature scalar across the boundary hypersurface of the star. The radial distribution of the physical quantities such as density, anisotropic pressure and radial heat flux are studied. The inhomogeneity of the collapsing interior leads to a non-zero acceleration. The divergence of this acceleration and the loss of energy through a heat conduction forces the rate of the collapse to die down and the formation of a zero proper volume singularity is realized only asymptotically.     

Direct evidence for CH···π interaction mediated stabilization of Pro-cisPro bond in peptides with Pro-Pro-aromatic motifs

Although weak interactions play subtle but important roles in dictating protein structures, their experimental detection is nontrivial. From NOE experiments we provide direct evidence for the presence of CH···π interaction, operational between the C(α)-H of the first Pro and the aromatic (Aro) side chain of Xaa, in a peptide series with the general sequence Ac-Pro-Pro-Xaa-NH(2). Indirect evidence of CH···π interaction is provided from ring current-induced upfield displacement of Pro(1) C(α)-H chemical shifts and restriction of side-chain (χ1) rotation of Xaa. A consequence of this interaction is the enhanced stability of the Pro-cisPro conformer in Ac-Pro-Pro-Xaa-NH(2) when Xaa is aromatic. The free energies associated with trans to cis transformation of the Pro-Pro moiety are 0.35, 0.59, 0.64, and 0.82 kcal/mol when Xaa is Tyr, Trp, Phe, and His (pH of 8.4), respectively. In comparison, the corresponding free energy is ～1.55 kcal/mol when Xaa is nonaromatic. The observed population of Pro-cisPro-His and the pH-induced perturbation of electron density of the His side chain were correlated, providing further evidence for a direct role of CH···π interaction in modulating the stability of Pro-cisPro population in Ac-Pro-Pro-Aro-NH(2). Our study establishes Pro-Pro-Aro to be a new sequence motif that can stabilize Pro-cisPro peptide bonds. This study not only identifies a new structurally biased sequence motif but also directly demonstrates the role played by CH···π interactions in subtly altering conformational preferences of three-residue peptide sequences with implications on the role played by cis-peptide bonds in unfolded proteins.