Eco‐friendly ionic liquid assisted capillary electrophoresis and α‐acid glycoprotein‐assisted liquid chromatography for simultaneous determination of anticancer drugs in human fluids

In the current work, two eco‐friendly analytical methods based on capillary electrophoresis (CE) and reversed phase liquid chromatography (RPLC) were developed for simultaneous determination of the most commonly used anticancer drugs for Hodgkin's disease: methotrexate (MTX), vinblastine, chlorambucil and dacarbazine. A background electrolyte (BGE) of 12.5 mmol/L phosphate buffer at pH 7.4 and 0.1 µmol/L 1‐butyl‐3‐methyl imidazolium bromide (BMImBr) ionic liquid (IL) was used for CE measurements at 250 nm detection wavelength, 20 kV applied voltage and 25 °C. The rinsing protocol was significantly improved to reduce the adsorption of IL on the interior surface of capillary. Moreover, RPLC method was developed on α‐1‐acid glycoprotein (AGP) column. Mobile phase was 10 mmol/L phosphate buffer at pH 6.0 (100% v/v) and flow rate at 0.1 mL/min. As AGP is a chiral column, it was successfully separated l ‐MTX from its enantiomer impurity d ‐MTX. Good linearity of quantitative analysis was achieved with coefficients of determinations (r²) >0.995. The stability of drugs measurements was investigated with adequate recoveries up to 24 h storage time under ambient temperature. The limits of detection were <50 and 90 ng/mL by CE and RPLC, respectively. The using of short‐chain IL as an additive in BGE achieved 600‐fold sensitivity enhancement compared with conventional Capillary Zone Electrophoresis (CZE). Therefore, for the first time, the proposed methods were successfully applied to determine simultaneously the analytes in human plasma and urine samples at clinically relevant concentrations with fast and simple pretreatments. Developed IL‐assisted CE and RPLC methods were also applied to measure MTX levels in patients’ samples over time. Copyright © 2014 John Wiley & Sons, Ltd.     

A short note on the entrainment and exit boundary conditions

An attempt is made to find out the suitable entrainment and exit boundary conditions in laminar flow situations. Streamfunction vorticity formulation of the Navier–Stokes equations are solved by ADI method. Two‐dimensional laminar plane wall jet flow is used to test different forms of the boundary conditions. Results are compared with the experimental and similarity solution and the proper boundary condition is suggested. The Kind 1 boundary condition is recommended. It consists of zero first derivative condition for velocity variable and for streamfunction equation, mixed derivative at the entrainment and exit boundaries. Copyright © 2005 John Wiley & Sons, Ltd.     

Extractive spectrophotometric determination of Cobalt(II) in synthetic and pharmaceutical samples using Cyanex 923.

Cyanex 923 has been proposed as a sensitive analytical reagent for the direct extractive spectrophotometric determination of cobalt(II). Cobalt(II) forms a blue-colored complex with Cyanex 923 in the organic phase. The maximum absorbance of the complex is measured at 635 nm. Beer's law was obeyed in the range 58.9 - 589.0 microg of cobalt. The molar absorptivitiy and Sandell's sensitivity of the complex was calculated to be 6.79 x 10920 l mol(-1) cm(-1) and 0.088 microg cm(-2), respectively. The nature of the extracted species was found to be Co(SCN)2 x 2S. An excellent linearity with a correlation coefficient value of 0.999 was obtained for the Co(II)-Cyanex 923 complex. Stability and regeneration of the reagent (Cyanex 923) for reuse is the main advantage of the present method. The method was successfully applied to the determination of cobalt in synthetic mixtures and pharmaceutical samples was found to give values close to the actual ones. Standard alloy samples, such as high-speed tool BCS 484 and 485, have been tested for the determination of cobalt for the purpose of validating the present method. The results of the proposed method are comparable with atomic absorption spectrometry and were found to be in good agreement.     

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione

NaBH₄ reduction of a cage dione proceeds in a stereospecific fashion to give theendo,endo-diol. This reactivity is related to the crystal structure.     

Characterization of surface deformation around Vickers indentations in InGaAsP epilayers on InP substrate

The deformation surrounding Vickers indentations on InGaAsP/InP epilayers have been studied in detail. The surface topography was characterized by using atomic force microscopy (AFM). The material pile-up and sink-in regions around the indentation impression was observed for the quaternary InGaAsP/InP epilayers. The sectional analysis mode of the AFM shows the depth profile at the indented region. Microindentation studies were carried out for different atomic fraction of the quaternary InGaAsP/InP compound semiconductor alloys. The microhardness values of InGaAsP/InP epilayers were found to be in the range of 5.08 and 5.73 GPa. These results show that the hardness value of the quaternary alloy drastically increases as the composition of As was increased by 0.01 atomic fraction and when the phosphorous concentration decreases from 0.4 to 0.38. The reason may be that the increase in As concentration hardens the lattice when phosphorous concentration was less and hardness decreases when phosphorous was increased.     

Critical phenomena in FINEMET alloy

The Fe_73.5Cu₁Nb₃Si_13.5B₉ FINEMET alloy has been prepared by the rapid solidification technique. The critical behaviour of this alloy in the amorphous as well as in its nanocrystalline states has been studied near their respective Curie temperatures. From the values of the critical exponents one can conclude that the alloy behaves like a 3D Heisenberg ferromagnet in the amorphous and nanocrystalline states. But there exists a slight increase in the value of β for the alloy annealed at 823 K (the nanocrystalline state) as observed in most of the amorphous alloys.     

Synchronized whistlers recorded at Varanasi

Some interesting events of synchronized whistlers recorded at low latitude station Varanasi during magnetic storm period of the year 1977 are presented. The dynamic spectrum analysis shows that the component whistlers are Eckersley whistlers having dispersion 10 s^1/2 and 30 s^1/2. An attempt has been made to explain the dynamic spectra using lightning discharge generated from magnetospheric sources     

Differentiators and the geometry of polynomials

In 1959, Davis introduced the concept of a differentiator of an operator on a finite-dimensional Hilbert space. We prove that every such operator possesses a differentiator. We also use the theory of differentiators to solve several problems in the geometry of polynomials. For instance, we answer in the affirmative a twenty year old unsolved conjecture of Schoenberg, a related conjecture of Katsoprinakis and a fifty year old unsolved conjecture of De Bruijn and Springer.     

Precise lattice parameter measurements in CsCl-Br solid solutions between room temperature and 90°K by powder x-ray diffraction

Solid solutions of CsCl-Br in five different concentrations were prepared in sealed quartz tubes by heating the mixture to 1123°K for 6–8 hr and quenching to room temperature. X-ray diffractograms were taken at eight different temperatures between room temperature and 90°K for these solid solutions using the YPC50NM powder diffractometer and a continuous flow cryostat. The observed lattice parameters for each sample at each temperature obtained from the powder diffractograms were then extrapolated to give the true lattice parameters using the least square method with Nelson-Riley extrapolation scheme. The values of the true lattice parameters at each concentration and at each temperature were tabulated and the results discussed. It is shown that the lattice parameters vs temperature for some concentrations exhibit an anomalous behaviour. Contribution No. 691     

SHI induced modification in CR-39 polycarbonate by positron annihilation lifetime studies

CR-39 is a polycarbonate widely used as SSNTD for recording nuclear charged particles and in other applications. Latent ion tracks produced in the polymers due to the damage produced by the passage of Swift Heavy Ions contain amorphous material with highest degree of disorder, changing the free volume properties which have strong correlation with the macroscopic properties of the material. Positron annihilation lifetime spectroscopy (PALS) provides direct information about the dimension, content and hole size distribution of free volume in polymers. The effect of irradiation of ⁴⁰Ar (14.9 MeV/n) ions on CR-39 polycarbonate by Positron Annihilation Lifetime Spectroscopy (PALS) is reported here. PALS provides a non-destructive and non-interfering probe, having high detection efficiency for free volume hole properties. From o-Ps lifetime mean free volume hole radius and average free volume of the micro-voids have been calculated. PAL measurement shows an increase in free volume on irradiation.