Comparison of HPLC and MEEKC for Miconazole Nitrate Determination in Pharmaceutical Formulation

A simple solid phase extraction (SPE) method coupled with high performance liquid chromatography (HPLC) using UV detector and microemulsion electrokinetic chromatography (MEEKC) has been developed and compared for the quantitative determination of miconazole nitrate in pharmaceutical formulation. For HPLC method, two parameters were optimized, namely, the wavelength and the mobile phases. The optimized condition was at the 225 nm wavelength and the mobile phase of ACN:MeOH (90:10 v/v). There are seven MEEKC parameters that were optimized, in this research, which were applied to voltage, temperature, wavelength, sodium dodecyl sulfate (SDS) concentration, buffer pH, buffer concentration and butan-1-ol concentration. The optimum MEEKC condition was obtained using 86.35 % (w/w) 2.5 mM borate buffer pH 9, 0.25 % (w/w) SDS, 0.8 % (w/w) ethyl acetate, 6.6 % w/w butan-1-ol and 6.0 % (w/w) acetonitrile. The combination of SPE using a diol column with HPLC–UV and the MEEKC methods were successfully applied for the determination of miconazole nitrate in a pharmaceutical formulation with the recovery percentage of 98.35 and 92.50 %, respectively.     

Intrinsic adsorption properties of CO2 on 5A and 13X zeolite

Data for the adsorption of CO₂ on 5A (CaA) and 13X (NaX) zeolite are critically evaluated. In addition, fresh data for the adsorption of CO₂ on 13X zeolite is reported. Three intrinsic properties are examined: q _max , the saturation loading, K _H , the Henry constant, and (?ΔH) _q , the isosteric heat of sorption. Below a reduced temperature T _r , of 0.9, the q _max values for both 5A and 13X zeolites are similar to theoretical values that may be derived using zeolitic crystallographic properties and the sorbate density calculated using the Rackett equation. For the region 0.9 ≤ Tr ≤ 1.0, the calculated q _max values exceed the theoretical values similarly calculated, indicating that the molecules have a smaller molar volume than in a similar liquid phase. This is a similar result to that observed in ionic liquids. Linear regressed equations are derived for q _max for the region 0.9 ≤ Tr ≤ 1.25. The Henry constant values for 5A are remarkably consistent for the five studies examined, with a correlation coefficient, R, of 0.999 for the van’t Hoff equation, but for the seven studies examined in 13X the data is more disperse as indicated by a correlation coefficient R of 0.899 for the van’t Hoff equation. The values of (?ΔH) _q , the isosteric heat of sorption are in agreement with the literature. An explanation is advanced for the discrepancy between the higher heats of sorption values obtained calorimetrically from those obtained from isosteric adsorption studies. Finally, the fresh data is observed to fit the Toth model with regression coefficients of 0.999. However, the parameters obtained for the Toth equation by regression are significantly different from the intrinsic properties derived earlier, indicating the difficulty of deriving intrinsic parameters from isotherm fits.     

Bulk polymer nanoparticles containing a tetrakis(3-hydroxyphenyl)porphyrin for fast and highly selective separation of mercury ions

We report on the synthesis of polymeric nanoparticles (PNPs) containing a tetrakis(3-hydroxyphenyl)porphyrin, and their use for the separation of mercury(II) ion. The PNPs were prepared by bulk polymerization from methacrylic acid (the monomer), ethyleneglycol dimethacrylate (the cross-linker), 2,2′-azobisisobutyronitrile (the radical initiator) and the mercury(II) complex of 5,10,15,20-tetrakis(3-hydroxyphenyl)-porphyrin. The Hg(II) ion was then removed by treatment with dilute hydrochloric acid. The PNPs were characterized by colorimetry, FT-IR spectroscopy, and scanning electron microscopy. The material is capable of binding Hg(II) from analyte samples. Bound Hg(II) ions can be eluted with dilute nitric acid and then quantified by cold vapor AAS. The extraction efficiency, the effects of pH, preconcentration and leaching times, sample volume, and of the nature, concentration and volume of eluent were investigated. The maximum adsorption capacity of the PNPs is 249 mg g^?1, the relative standard deviation of the AAS assay is 2.2 %, and the limit of detection (3σ) is 8 ng.L^?1. The nanoparticles exhibit excellent selectivity for Hg(II) ion over other metal ions and were successfully applied to the selective extraction and determination of Hg(II) ion in spiked water samples.

Preparation of activated carbon filled epoxy nanocomposites

Activated carbon derived from oil palm empty fruit bunch (AC-EFB), bamboo stem (AC-BS), and coconut shells (AC-CNS) were obtained by pyrolysis of agricultural wastes using two chemical reagents (H₃PO₄ or KOH). The AC-EFB, AC-BS and AC-CNS were used as filler in preparation of epoxy nanocomposites. Epoxy nanocomposites prepared at 1, 5 and 10 % activated carbons filler loading using KOH and H₃PO₄ chemical agents. Transmission electron microscopy confirms better dispersion of the nano-activated carbons in the epoxy matrix at 5 % activated carbon. The presence of 5 % AC-CNS in the epoxy matrix using H₃PO₄ chemical reagent resulted in an improvement of the thermal stability of epoxy matrix. KOH treated AC filled epoxy nanocomposites were slightly better in thermal stability as compared to H₃PO₄ treated AC filled epoxy nanocomposites, may be due to better interaction of filler with epoxy matrix. Thermal analysis results showed that thermal stability of the activated carbon filled epoxy nanocomposites improved as compared to the neat epoxy matrix. The degree of crystallinity of epoxy matrix was improved by adding the activated carbon due to interfacial interaction between AC and epoxy matrix rather than loading of AC alone. Developed nanocomposites from biomass (agricultural wastes) materials will help to reduce the overall cost of the materials for its demanding applications as insulating material.     

Synthesis of novel di-Se-containing thymidine and Se-DNAs for structure and function studies

The selenium derivatization of nucleic acids and nucleic acid-protein complexes has provided a powerful tool to solve phase problem in X-ray crystallography.Selenium atoms in the nucleotides can serve as fine scattering centers in crystal diffraction.Towards the synthesis of multiple selenium atom-containing nucleotides,which offers strong phasing power to facilitate crystal structure determination,we report here the synthesis of the thymidine analogue containing two Se atoms in one nucleobase.The novel Se-containing nucleoside and oligonucleotide DNAs were synthesized and found with the red-shifted UV spectrum and yellow color.Their unique properties are useful in phase determination,nucleic acid-based detection as well as spectroscopic studies of nucleic acids and nucleic acid-protein complexes.     

In vitro surface biocompatibility of high-content silicon-substituted calcium phosphate ceramics

The present work investigates surface biocompatibility of silicon-substituted calcium phosphate ceramics. Different silicon-substituted calcium phosphate ceramic bodies were prepared from co-precipitated powders by sintering at 1300°C. The in vitro bioactivity of the ceramics was assessed in simulated body fluid (SBF) at 37°C for periods up to 4 weeks. The changes in the surface morphology and composition were determined by scanning electron microscopy (SEM) coupled with electron probe microanalysis and energy dispersive spectrometer (EDX). Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used to observe the change in ionic concentration of SBF after removal of the samples. The bioactivity of the ceramics increased with an increasing silicate ion substitution in a systematic way. The surface of ceramics with 2.23% silicon substitution was partially covered with apatite layer after one week, while ceramics with 8.1% silicon substitution were completely covered with apatite in the first week. The porous microstructure of high-concentration Si-substituted ceramics helps the dissolution of surface ions and the leaching process. This allows SBF to reach supersaturation in a short time and accelerate the deposition of apatite layer.      

Reactive intermediates in the reaction of hydrazinecarbothioamides with 2-(bis(methylthio)methylene)malononitrile and ethyl 2-cyano-3,3-bis(methylthio)acrylate

Research on Chemical Intermediates - The reaction of N-substituted hydrazinecarbothioamides with both 2-(bis(methylthio)methylene)malononitrile and ethyl 2-cyano-3,3-bis(methylthio)acrylate...     

Polyaniline immobilized on polycaprolactam nanofibers as a sorbent in electrochemically controlled solid-phase microextraction coupled with HPLC for the determination of angiotensin II receptor antagonists in human blood plasma

In this research, electrospun polycaprolactam nanofibers were collected on a fine stainless steel mesh sheet without a binder, and a layer of conductive polyaniline was chemically deposited on the nanofibers. The polyaniline immobilized on the polycaprolactam nanofibers provided high electrical conductivity, acceptable mechanical stability, and a large surface area. This assembly was then used as a working electrode in electrochemically controlled solid-phase microextraction (EC-SPME), a fast and environmentally friendly method. The polymer layers were characterized by SEM and FTIR techniques. Significant factors affecting the EC-SPME efficiency were investigated, including the desorption conditions, the sorbent used, the pH of the sample solution, the extraction voltage, the extraction time, and the ionic strength. Under the optimum conditions, the limits of detection and quantification for the target analytes were 0.9–1.8 μg L⁻¹ and 3.0–6.1 μg L⁻¹, respectively. The linear dynamic range was 5–2000 μg L⁻¹, with R² > 0.993. The method was coupled with HPLC analysis and applied to the determination of angiotensin ΙΙ receptor antagonists (ARA-ΙΙs) in human plasma, and relative recoveries of 91.1–104.3% with RSDs of ≤8.3% were obtained.

     

Synthesis,characterization and cytotoxicity of new 2‐isonicotinoyl‐N‐phenylhydrazine‐1‐carbothioamide and its metal complexes

The reaction of the newly synthesized ligand, 2‐isonicotinoyl‐N‐phenylhydrazine‐1‐carbothioamide (H₃L), with acetate salt of Co (II), Cu (II),Ni (II) and Zn (II) led to isolation of four solid complexes. The ligand and complexes structure elucidation were based on elemental analyses, spectral analyses (IR, UV–Visible, ¹H and¹³C‐NMR, MS and ESR), TGA, molar conductivity and magnetic moments measurements. The results indicated that the ligand exists in the thioketo form, while on coordination to the metal ions; it behaves as mono‐negative bidentate chelate and exists in enol form. The optical band gap measurements of the ligand and its metal complexes are in the range 3.83–4.48 eV indicating their semi‐conducting character. The cytotoxicity examination of H₃L and its Zn (II) complex showed that the ligand have very strong cytotoxicity against both HCT‐116 and HEPG‐2 cell lines while, Zn (II) complex has moderate activity.     

Unanticipated Heterocyclization from Reaction of Hydrazine Hydrate and/or Hydrazine Dihydrochloride with 1‐Ethyl‐4‐hydroxyquinolin‐2(1H)‐one

Unexpectedly, the reaction of 1‐ethyl‐4‐hydroxyquinolin‐2(1H)‐one ( 1 ) with hydrazine hydrate and/or hydrazine dihydrochloride led to three different products. In addition to the expected quninolinylhydrazine, two heteropentacycles, diquinopyrrole and diquinopyridazine, were afforded, depending on reaction conditions. The structure of the new products was established upon their spectral and analytical data.