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.     

Surfactant-induced aggregation patterns of thiazole orange: a photophysical study

The aggregation behavior of the DNA marker dye thiazole orange (TO), has been investigated in two types of surfactant assemblies, namely, premicelles/micelles of sodium dodecyl sulfate (SDS) and pre reverse micelles/reverse micelles of sodium bis(2-ethylhexyl) sulfosuccinate (AOT). In the case of an SDS/water system, absorption spectral changes of TO signify the formation of H-aggregates and H-dimers of the dye at premicellar concentrations, which subsequently convert to the monomeric form beyond the critical micellar concentration (cmc). Interestingly, the observed changes in the absorption and emission characteristics due to the surfactant-induced formation of H-aggregates/dimers of TO are found to be useful to estimate the surfactant concentration parameters for premicellar aggregation of SDS. In the case of an AOT/n-heptane system, similarly, H-aggregates/dimers are observed at low AOT concentrations, below the cmc. However, in this case, the H-dimers persist even beyond the cmc. This is attributed to the strong tendency of TO for self-aggregation and its favorable electrostatic interactions with the AOT head groups. With increasing water content in the AOT reverse micelles, the hydration of the dye leads to the conversion of H-dimers to the monomeric form. The steady-state fluorescence results are nicely corroborated with those from time-resolved fluorescence studies and demonstrate the interesting behavior of the surfactant-induced aggregation of TO dye.     

Surface functionalized silver nanoparticle conjugates: demonstration of uptake and release of a phototherapeutic porphyrin dye

A facile supramolecular approach to prepare surface functionalized silver nanoparticle conjugates has been established and their enhanced molecular recognition features have been explored to demonstrate the uptake and stimulus responsive release of a phototherapeutic porphyrin dye, the TMPyP.     

A facile approach for morphosynthesis of Pd nanoelectrocatalysts

A facile approach has been developed for synthesis of highly-structured, anisotropic Pd nanostructures. The dendritic Pd nanostructures show superior performance toward oxidation of formic acid and methanol for fuel cell application.     

Wettability Alteration Mechanism for Oil Recovery from Fractured Carbonate Rocks

Oil can be recovered from fractured, initially oil-wet carbonate reservoirs by wettability alteration with dilute surfactant and electrolyte solutions. The aim of this work is to study the effect of salinity, surfactant concentration, electrolyte concentration, and temperature on the wettability alteration and identify underlying mechanisms. Contact angles, phase behavior, and interfacial tensions were measured with two oils (a model oil and a field oil) at temperatures up to 90°C. There exists an optimal surfactant concentration for varying salinity and an optimal salinity for varying surfactant concentration at which the wettability alteration on an oil-aged calcite plate is the maximum for anionic surfactants studied. As the salinity increases, the extent of maximum wettability alteration decreases; also the surfactant concentration needed for the maximum wettability alteration decreases. IFT and contact angle were found to have the same optimal salinity for a given concentration of anionic surfactants studied. As the ethoxylation increases in anionic surfactants, the extent of wettability alteration on calcite plates increases. Wettability of oil-aged calcite plates can be altered by divalent ions at a high temperature (90°C and above). Sulfate ions alter wettability to a greater extent in the presence of magnesium and calcium ions than in the absence. A high concentration of calcium ions can alter wettability alone. Magnesium ions alone do not change calcite plate wettability. Wettability alteration increases the oil recovery rate from initially oil-wet Texas Cordova Cream limestone cores by imbibition.     

Spin-orbit interaction in molecular photoelectron spectra An intermediate coupling approach

A new and general semiempirical method for calculating ionization energies of molecules containing heavy atoms is presented. The extended Hückel hamiltonian is amended with a phenomenological one-electron spin-orbit interaction operator, and ionization energies are equated to orbital energies according to Koopmans' theorem. Calculations are presented for molecules with Br and I as heavy atoms. The systems considered are the hydrogen halides, diatomic halogens and interhalogens, haloacetylenes, halomethanes, and boron trihalides. Good agreement with the observed spin-orbit splitting is obtained. New assignments are proposed for the trihalides considered.     

Numerical solution of minimax problems of optimal control,part 2

In a previous paper (Part 1), we presented general transformation techniques useful to convert minimax problems of optimal control into the Mayer-Bolza problem of the calculus of variations [Problem (P)]. We considered two types of minimax problems: minimax problems of Type (Q), in which the minimax function depends on the state and does not depend on the control; and minimax problems of Type (R), in which the minimax function depends on both the state and the control. Both Problem (Q) and Problem (R) can be reduced to Problem (P).In this paper, the transformation techniques presented in Part 1 are employed in conjunction with the sequential gradient-restoration algorithm for solving optimal control problems on a digital computer. Both the single-subarc approach and the multiple-subarc approach are employed. Three test problems characterized by known analytical solutions are solved numerically.It is found that the combination of transformation techniques and sequential gradient-restoration algorithm yields numerical solutions which are quite close to the analytical solutions from the point of view of the minimax performance index. The relative differences between the numerical values and the analytical values of the minimax performance index are of order 10^–3 if the single-subarc approach is employed. These relative differences are of order 10^–4 or better if the multiple-subarc approach is employed.This research was supported by the National Science Foundation, Grant No. ENG-79-18667, and by Wright-Patterson Air Force Base, Contract No. F33615-80-C3000. This paper is a condensation of the investigations reported in Refs. 1–7. The authors are indebted to E. M. Coker and E. M. Sims for analytical and computational assistance.     

Electron transfer reactions of V(IV) with Cl(I), Br(I) and I(I). A kinetic study

A kinetic study on the oxidation of V(IV) by chloramine-T (CAT) at pH 6.85 by N-bromo succinimide (NBS) in aqueous acetic acid–perchloric acid media and by N-iodo succinimide (NIS) in aqueous perchloric acid medium has been carried out. In all the systems studied the order with respect to the oxidant is unity. NBS and CAT oxidation reactions exhibited Michaelis–Menten type kinetics, and the NIS study indicated unit dependence on [substrate]. Independence on acidity has been observed in the case of CAT and NBS reactions, but NIS reactions exhibited inverse unit dependence on [acid]. Novel solvent influences have been noticed in the case of CAT reactions, but with NIS and NBS reactions retardation in the rate has been observed with an increase in the percentage of acetic acid. Plausible mechanisms consistent with the results have been postulated, and suitable rate laws in consonance with the postulated mechanisms have been derived.     

The effect of exchange in autoionization processes

The effect of including distortion (with and without exchange) in the wavefunction for the continuum electron while calculating the probability of autoionization of 2s ^{2 1} S. 2s2p ^1,3 P, 2p ^{2 1} D and 2p ^{2 1} S states of He and Li⁺ has been studied.