Studies towards iodine-catalyzed dehydrative-cycloisomerization of pent-4-yne-1,2-diols to di- and tri-substituted furans

An efficient and single-step iodine catalyzed and metal-free synthesis of di and tri-substituted 2-methylfuran derivatives were achieved from 1-popargyl-1,2-diols. Stereospecific synthesis of starting 1,2-diols was achieved by indium mediated Barbier type propargylation on corresponding keto-alcohols or by sodium borohydride mediated reduction of 2-hydroxy-2-propargyl ketones. The furan synthesis proceeded through iodine mediated 5-exo-trig cyclization, dehydration and reductive deiodination. The method was applied to the synthesis of 2-methylfuran fused to phenanthrene, pyrene and acenaphthylene rings.     

Effect of bovine serum albumin on the surface properties of ionic liquid-type Gemini surfactant

The effect of bovine serum albumin on the surface properties of IL-type gemini surfactant ([C₁₀-4-C₁₀im]Br₂), have been investigated by surface tension method. The critical micelle concentration (CMC) as a function of BSA concentrations at various temperatures was investigated. The CMC of [C₁₀-4-C₁₀im]Br₂ increases with increasing the concentration of BSA as well as the temperature of the system. The interfacial parameters viz; maximum surface excess concentration (Γ_max), the minimum area per molecule (A_min), and surface pressure at CMC (Π_cmc) were calculated. In addition, thermodynamic parameters of adsorption and micellization were evaluated by using surface tension data. The results indicated that the binding of [C₁₀-4-C₁₀im]Br₂ to BSA is spontaneous and exothermic in nature. The process is entropy driven and hydrophobic interactions are the major driving forces.     

Integrated quality by design (QbD) and design of experiments (DoE) approach for UFLC determination of telaprevir in rat serum

An ultrafast liquid chromatographic bioanalytical method was developed and validated for the determination of telaprevir in Wistar albino rat serum. Principles of quality by design (QbD) were implemented for enhancing the bioanalytical liquid–liquid extraction of telaprevir from rat serum. A Box–Behnken design was utilized in the studies by selecting extraction time, centrifugation speed, and vortex time as the critical method variables for evaluating their effect on the critical analytical attribute, i.e., %recovery of telaprevir. Chromatographic separation was achieved within a run time of 10?min using a C-18 column and mobile phase comprising of methanol:borate buffer of pH 9 (90:10 v/v) flowing at 1.2?mL/min. Photodiode array detection was performed at 270?nm. Results of validation studies were satisfactory. The method was linear over a concentration of 25–10,000?ng/mL. Limit of detection for the developed method was 10?ng/mL. Further, design of experiments (DoE) used for inter-day accuracy and precision study suggested superior method reliability. This integrated QbD- and DoE-based approach ensured the development of a validated and reliable analytical method for optimum bioanalysis of telaprevir in biological matrix.     

One pot three component synthesis of spiro [indolo-3,10’-indeno[1,2-b]quinolin]-2,4,11’-triones as a new class of antifungal and antimicrobial agents

A simple and efficient three component procedure has been developed for the synthesis of highly substituted spiro[indolo-3,10'-indeno[1,2-b]quinolin]-2,4,11'-triones by one pot three component condensation of enaminones, isatin and indane-1,3-dione in ethanol:water (1:1) in presence of ceric ammonium nitrate (CAN) as catalyst. This method provides several advantages such as lesser reaction time, high yield of products and operational simplicity. The antimicrobial activity of some of the compounds has been investigated against six microbial strains, some of the tested compounds showed good antimicrobial activity.     

Measurement and Modeling of Phase Equilibrium,Volumetric Properties and Molar Refractivity of 2-Methylpropan-2-ol + Ethane-1,2-diol

2-Methylpropan-2-ol, an important fine chemical, may be dehydrated during extractive distillation with glycols as entrainer. Experimental isobaric phase equilibrium studies were carried out on binary mixtures of 2-methylpropan-2-ol with ethane-1,2-diol, as an entrainer, at the local atmospheric pressure of 94.99 kPa and at sub-atmospheric pressures of 19.99, 39.99, 59.99, 78.79 kPa using a Sweitoslawski-type ebulliometer. The Wilson and NRTL activity coefficient models were used to correlate the experimental results and the binary interaction parameters were obtained using the Generalized Reduced Gradient optimization technique. UNIFAC was also used to predict the deviations in bubble temperatures. Moreover, the variation in density, refractive index values and other derived properties (excess molar volumes, partial molar volumes and deviations in molar refractivity) were explored at 303.15, 313.15, 323.15 and 333.15 K to understand the shift of equilibrium with the variation in the mixture composition for the conformational state of the molecules. The Redlich–Kister polynomial equation was used to correlate the excess molar volumes and deviations from molar refractivity. Different theoretical mixing rules (Lorentz–Lorenz, Wiener, Heller, Gladstone–Dale and Arago–Biot) are investigated and reported in terms of average percentage deviation. Furthermore, the Prigogine–Flory–Patterson theory was used to predict the trend of the dependence of excess molar volumes on composition for the present system.     

Speciation and Multinuclear NMR Spectroscopic Studies of Di- and Trimethyltin(IV) Moieties with MESNA in Aqueous Medium

The interaction of Me₂Sn(IV)²⁺ and Me₃Sn(IV)⁺ with a prodrug, sodium 2-mercaptoethane sulfonate (HSCH₂CH₂SO₃Na, MESNA) abbreviated as (HL), has been studied potentiometrically in aqueous solution (I = 0.1 mol·L^?1 KNO₃, 298 K). The concentration distribution of various species formed in the solution was studied with changes in pH (~3–11). A strong coordination of MESNA with metal through the S atom of thiol group has been found. In the Me₂Sn(IV)–HL system, the species [Me₂Sn(L)]⁺ (53.1–75.6%) is predominant at acidic pH (3.73 ± 0.02) and the species [Me₂Sn(L)₂OH]^? (29.4–38.5%) is predominant at basic pH (10.32 ± 0.08). In contrast, for the Me₃Sn(IV)⁺ system, [Me₃SnL] (37.0–57.4%) is the major species at pH 7.65 ± 0.03 and [Me₃Sn(OH)] (49.9–67.2%) and [Me₃Sn(L)(OH)]^? (30.2–46.5%) are the major species at pH 11.05 ± 0.01. However, at physiological pH (7.01 ± 0.32), in both (1:1) and (1:2) Me₂Sn(IV)–HL systems, the species [Me₂Sn(L)(OH)] (67.2–89.9%) is predominant, whereas for Me₃Sn(IV)–HL (1:1) and (1:2) systems, [Me₃Sn(OH)] (53.5%) and [Me₃SnL] (56.8%) are the respective predominant species. In order to characterize the possible geometry of the proposed complex species, multinuclear (¹H, ¹³C and ¹¹⁹Sn) NMR studies were carried out at different pHs. No polymeric species were detected in the experimental pH range.     

Slow magnetohydrodynamic flow past a circular cylinder

Oseen’ approximations are used to study the slow motion of a viscous, incompressible, electrically conducting fluid past a circular cylinder in the presence of a uniform aligned magnetic field. Using series truncation method, the analytical solutions for the first three terms in the Fourier sine series expansion of the stream function are obtained. Numerical values of the tangential drag for different values of magnetic interaction parameter and viscous Reynolds number are calculated.     

A parameter-uniform scheme for singularly perturbed partial differential equations with a time lag

A numerical scheme for a class of singularly perturbed delay parabolic partial differential equations which has wide applications in the various branches of science and engineering is suggested. The solution of these problems exhibits a parabolic boundary layer on the lateral side of the rectangular domain which continuously depends on the perturbation parameter. For the small perturbation parameter, the standard numerical schemes for the solution of these problems fail to resolve the boundary layer(s) and the oscillations occur near the boundary layer. Thus, in this paper to resolve the boundary layer the extended cubic B-spline basis functions consisting of a free parameter λ are used on a fitted-mesh. The extended B-splines are the extension of classical B-splines. To find the best value of λ the optimization technique is adopted. The extended cubic B-splines are an advantage over the classical B-splines as for some optimized value of λ the solution obtained by the extended B-splines is better than the solution obtained by classical B-splines. The method is shown to be first-order accurate in t and almost the second-order accurate in x. It is also shown that this method is better than some existing methods. Several test problems are encountered to validate the theoretical results.     

A mathematical model to characterise effects of liquid hold-up on bosh silicon transport in the dripping zone of a blast furnace

A first principle based mathematical model has been developed to characterise the effect of total liquid hold-up on the bosh silicon distribution behaviour in the dripping zone of a blast furnace. Two specific cases of hold-up behaviour have been investigated, namely, hold-up in the absence and in the presence of counter current gas flow conditions. The model exemplifies coupled phenomenon of chemical kinetics, transport processes and liquid hold-up to characterise the silicon behaviour in the dripping zone. The present modelling investigation shows that the bosh silicon level diminishes with the enhanced liquid hold-up in the dripping zone. Further, the influence of counter current gas flow on the hold-up is not significant. However, it has been observed that the liquid phase temperature reduces with increased liquid hold-up in dripping zone under steady state operating conditions. The model predictions of bosh silicon distribution have been validated with the published literatures (bulk values) and found to be in good agreement.