Ring currents in condensed ring systems

We have studied magnetism and aromaticity of polycyclic ring systems by analyzing ring currents for different circulations in these molecules. The technique employed for calculating ring currents uses correction vectors which implicitly includes all the eigenstates of the Hamiltonian in the space of the chosen configurations. We have employed the Pariser–Parr–Pople Hamiltonian and have carried out full configuration interaction (CI) calculations for small systems and approximate CI calculations for large systems. The systems studied include polyacenes, nonaromatic ring systems including the C₆₀ fragments pyracylene, fluoranthene, and corannulene, and heteroatomic systems with upto two six-membered rings. We find that in polyacenes, the aromaticity of the extreme phenyl rings reduces with increasing number of phenyl rings in the system, and it saturates at ≈⅔ the benzene value. In systems containing nonaromatic rings, we find paramagnetic or diamagnetic behavior for different circulations depending upon the number of atoms in the chosen ring cycle, in agreement with the 4n+2 rule. In corannulene, the largest fragment of C₆₀ we have studied, the five-membered ring is weakly diamagnetic while the six-membered ring is more diamagnetic, although much less than in isolated benzene. The ring structures with heteroatoms studied are pyridine, pyrimidine, and its isomers, s-triazine, quinoline and its isomer, and quinazoline and its isomers. All these have similar ring currents as in their purely carbon counterparts, although ions of these molecules show interesting behavior. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 503–513, 1998     

An unusual synthesis of 3-(2-(arylamino)thiazol-4-yl)-2H-chromen-2-ones from ethyl 2-(chloromethyl)-2-hydroxy-2H-chromene-3-carboxylate via benzopyran ring opening

An unusual and unexpected synthesis of 3-(2-(arylamino)thiazol-4-yl)-2H-chromen-2-ones has been observed by the reaction of ethyl 2-(chloromethyl)-2-hydroxy-2H-chromene-3-carboxylate with various arylthioureas in ethanol under mild reaction conditions with excellent yields. The ambiguity in the structure of the obtained products has been solved by recording its single-crystal X-ray analysis. This protocol has been found to be a novel approach for the preparation of title compounds via benzopyran ring opening. A systematic plausible mechanism has been proposed for the formation of the product. Also, an efficient one-pot three-component method has been demonstrated for the formation of title compounds starting from salicylaldehyde.

     

Influence of container material on the heat transfer characteristics of nanofluids

The average and local thermal conductivity measurements of water-based Ag-nanofluid held in polypropylene and metallic containers using transient hot-wire method revealed a new phenomenon. The local thermal conductivity of water-based Ag nanofluid measured at different locations of containers was found to depend strongly upon the metallic container, but not on the polypropylene container. Similar observations have been found in water-based NiAl nanofluid, but not in water-based Al₂O₃ nanofluid. In contrast, this phenomenon was not observed for ethylene glycol-based Ag nanofluid, possibly due to the insignificant charge on the container wall, which partly explains the diversity in thermal conductivity by different researchers.     

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.     

Intermediate scale inflation and metastable supersymmetry breaking

We investigate the possibility of obtaining a low scale of supersymmetry breaking within the ISS framework using a metastable vacuum. This is achieved by introducing an R   symmetry preserving gravitational coupling of the ISS sector to a relatively low scale inflationary sector. We find the allowed range for the supersymmetry breaking scale, ¹⁰⁴ GeV?μ?¹⁰⁸ GeV${10}^4\text{GeV}?\mu ?{10}^8\text{GeV}$, which is low enough to be amenable to gauge supersymmetry breaking mediation. This scenario is based upon a so-called hilltop inflation phase whose initial condition problem is also addressed.     

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.     

Structural and magnetic inhomogeneities,phase transitions, 55Mn nuclear magnetic resonance,and magnetoresistive properties of La0.6 − x Nd x Sr0.3Mn1.1O3-δ ceramics

The structure, lattice imperfection, and properties of ceramic samples La_{0.6 ? x} Nd _x Sr_0.3Mn_1.1O_3-δ (x = 0–0.4) have been investigated using the X-ray diffraction, resistive, magnetic (χ_ac, ⁵⁵Mn NMR), magnetoresistive and microscopic methods. It has been shown that there is a satisfactory agreement between the concentration decrease in the lattice parameters a of the rhombohedral (x = 0, 0.1, 0.2) and cubic (x = 0.3, 0.4) perovskite structures and the average ionic radii $\bar R$ for the lattice containing anion vacancies, cation vacancies, and nanostructured clusters with Mn²⁺ ions in A-positions. With an increase in the neodymium concentration x, the vacancy-type imperfection increases, the cluster-type imperfection decreases, the temperatures of metal-semiconductor phase transition T _ms and ferromagnetic-paramagnetic phase transition T _C decrease, and the content of the ferromagnetic phase decreases. The anomalous hysteresis is associated with the appearance of unidirectional exchange anisotropy induced in a clustered perovskite structure consisting of a ferromagnetic matrix and a planar antiferromagnetic cluster coherently coupled with it. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra has revealed a high-frequency electronic double exchange (Mn³⁺-O^2?-Mn⁴⁺) ? (Mn⁴⁺-O^2?-Mn³⁺) and an inhomogeneity of the magnetic and charge states of manganese due to the heterogeneous environment of the manganese ions by other ions and defects. The observed changes in the resonant frequency and width of the resonance curve are caused by changes in the ratio Mn³⁺/Mn⁴⁺ and magnetic inhomogeneity. An increase in the neodymium concentration x leads to a decrease in the ferromagnetic phase content determined from the dependences 4πNχ_ac(T) and the ⁵⁵Mn NMR curves. The phase diagram characterizes an interrelation between the composition, the imperfection of the structure, and the transport, magnetic, and magnetoresistive properties of lanthanum neodymium manganite perovskites. It has been found that there is a correlation between the imperfection, magnetic inhomogeneity, coercive force, and magnetoresistance effect exhibited by the perovskite structure.     

Imperfection of the clustered perovskite structure, phase transitions, and magnetoresistive properties of ceramic La0.6Sr0.2Mn1.2 ? x Ni x O3 ± δ (x = 0–0.3)

Ceramic samples of lanthanum strontium manganite perovskites La_0.6Sr_0.2Mn_{1.2 ? x} Ni _x O_{3 ± ??} (0 ?? x ?? 0.3) have been investigated using the X-ray diffraction, magnetic (??_ac), ⁵⁵Mn NMR, resistive, and magnetoresistive methods. The specific features of the influence of the composition on the structure and properties of nonstoichiometric manganite perovskites have been established. It has been found that the rhombohedrally (R $\bar 3$ c) distorted perovskite structure contains cation and anion vacancies, as well as nanostructured clusters with Mn²⁺ ions in the A-positions. The substitution of Ni³⁺ ions (r = 0.74 ?) for Mn³⁺ ions (r = 0.785 ?) leads to a decrease in the lattice parameter a, the ferromagnetic-paramagnetic phase transition temperature T _C, and the metal-semiconductor phase transition temperature T _ms due to the disturbance of the superexchange interactions between heterovalent manganese ions Mn³⁺ and Mn⁴⁺. The observed anomalous magnetic hysteresis at 77 K has been explained by the antiferromagnetic effect of the unidirectional exchange anisotropy of the ferromagnetic matrix structure on the magnetic moments of the superstoichiometric manganese Mn²⁺ ions located in nanostructured planar clusters. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra of the compounds has revealed a high-frequency electronic superexchange of the ions Mn³⁺ ? O^2? ? Mn⁴⁺; a local heterogeneity of their surrounding by other ions, vacancies, and clusters; and a partial localization of Mn⁴⁺ ions. The local hyperfine interaction fields on ⁵⁵Mn nuclei have been determined. The concentration dependences of the activation energy and charge hopping frequency have confirmed that the Ni ions decrease the electrical conductivity due to the weakening of the electronic superexchange Mn³⁺ ? O^2? ? Mn⁴⁺. Two types of magnetoresistive effects have been found: one effect, which is observed near the phase transition temperatures T _C and T _ms, is caused by scattering at intracrystalline nanostructured heterogeneities, and the other effect, which is observed in the low-temperature range, is induced by tunneling through intercrystalline mesostructured boundaries. The phase diagram has demonstrated that there is a strong correlation between magnetic and electrical properties in rare-earth manganites.