Determination of neomycin and oxytetracycline in the presence of their impurities in veterinary dosage forms by high-performance liquid chromatography/tandem mass spectrometry

Two HPLC/MS/MS methods, one for determination of neomycin sulfate and the other for determination of oxytetracycline hydrochloride in the presence of their impurities, were developed and validated. Separations were achieved with gradient elution on a C18 column. All components were ionized by positive-ion electrospray and detected by multiple reaction monitoring. Calibration curves were linear, with correlation coefficients >0.99. Precision of the methods was confirmed by RSD values of 0.34 and 0.71% for neomycin and oxytetracycline, respectively. Recovery values of 101.5 and 101.0%, respectively, indicated adequate accuracy. Analysis time for neomycin was 24 min, with the retention time of the main compound at 10.1 min; for oxytetracycline, the analysis time was 18 min, with the main peak at 9.95 min. Longer retention times than expected were a consequence of the necessity of chromatographic separation of isomers with the same ion transition. All impurities defined in the pharmacopoeias were determined and their identities confirmed. The methods were tested for QC of veterinary dosage forms (commercial powders and injections containing these antibiotics).     

Micellar electrokinetic capillary chromatography determination of zinc bacitracin and nystatin in animal feed

An MEKC procedure was developed for the separation of zinc bacitracin (Zn-BC) and nystatin (NYS) in mixtures and in animal feedstuff. The running buffer was 15 mM borate/19 mM phosphate, pH 8.2, containing 20 mM SDS and 10% v/v methanol. Samples were run at 25 degrees C, the applied voltage was 25 kV, and an additional pressure of 5 mbar was applied. Both analytes were detected by UV simultaneously at 215 nm, Zn-BC alone at 192 and 254 nm, and NYS alone at 305 nm. The method was shown to be specific, accurate (recoveries were 100.0 +/- 0.6% and 100.1 +/- 0.6% for Zn-BC and NYS, respectively), linear over the tested range (correlation coefficients 0.9991 and 0.9994), and precise (RSD below 1.3% for both analytes). The method was applied to determine Zn-BC and NYS as additives in animal feed.     

Learning to be an opportunistic word problem solver: going beyond informal solving strategies

Informal strategies reflecting the representation of a situation described in an arithmetic word problem mediate students’ solving processes. When the informal strategies are inefficient, teaching students to make way for more efficient ways to find the solution is an important educational issue in mathematics. The current paper presents a pedagogical design for arithmetic word problem solving, which is part of a first-grade arithmetic intervention (ACE). The curriculum was designed to promote adaptive expertise among students through semantic analysis and recoding, which would lead students to favor the more adequate solving strategy when several options are available. We describe the ways in which students were taught to engage in a semantic analysis of the problem, and the representational tools used to favor this conceptual change. Within the word problem solving curriculum, informal and formal solving strategies corresponding to the different formats of the same arithmetic operation, were comparatively studied. The performance and strategies used by students were assessed, revealing a greater use of formal arithmetic strategies among ACE classes. Our findings illustrate a promising path for going past informal strategies on arithmetic word problem solving.

     

A two‐step procedure for clustering time varying data

The aim of this paper is to enlarge the usual domain of cluster analysis. A procedure for clustering time varying data is presented which takes into account the time dimension with its intrinsic properties.

This procedure consists of two steps. In the first step a dissimilarity between variables is defined and the dissimilarity matrix is calculated for each unit separately. In the second step the dissimilarity between units is calculated in terms of the dissimilarity matrices defined in the first step. The dissimilarity matrix obtained is the base for a suitable clustering method.

The procedure is illustrated on an empirical example.     

Tailoring thermal development of gamma alumina sorbents material using combustion synthesis: the effect of amino acids (G,A, N) and equivalence ratio

Using a combustion synthesis, the range of achievable textures is broader than using conventional synthesis methods and can be controlled more successfully. As a tool allowing the achievement and control of desired textures, here we bring about wet chemistry synthesis using aluminium nitrate nonahydrate (ANN) precursor systematically combined with different fuels (amino acids). The amino acids; glycine (G), alanine (A) and asparagine (N) have been specifically selected in order to show the role of gradual increase in their: (1) molar mass, (2) enthalpy of combustion, (3) amine groups content and (4) ratio to ANN. Detailed (micro) structural and thermal characterisations confirm that the nanocrystalline character and thermomechanical stability were not diminished in the course of this synthesis. The conditions leading to development of different morphologies from gels to powders were found to be heavily under the influence of fuel/oxygen ratio, i.e. of the smouldering versus flaming mechanism of the combustion. Higher content of nitrates (predominately from amino-rich amino acids) strongly promoted auto-combustion behaviour. As-derived alumina precursors have been thermally treated at various temperatures (quenched and soaked), to monitor γ- and α-alumina crystallisation, with respect to the development of morphology. Different texture types have been observed, such as porous wormhole, porous and porous expanded flakes. Higher fuel levels promote specific surface increase. This combustion synthesis allows facile tailoring of nanocrystalline γ-alumina with different morphological features, whereas samples having optimal parameters were suitable for catalyst support application on behalf of rapid sorption performance.

     

SPE and large-volume sample stacking in MEKC for determination of doxycycline in biological fluids: comparison of direct injection to SPE-MEKC

A novel and simple method has been developed for the determination of doxycycline (DOX) in biological fluids. The method is based on SPE, large-volume sample stacking (LVSS) and MEKC with UV-DAD detection. Six SPE cartridges have been used in investigation for sample clean up and pre-concentration (Supelco LC-8, LC-18, LC-SCX, and LC-WCX, as well as Strata-X and X-C). DOX was determined on a 56 cm (effective length 50 cm) x 50 microm id fused-silica capillary. The BGE was 20 mM borate buffer, pH 9.3, containing 80 mM SDS and 7.5% v/v of methanol (30 sx50 mbar), and the temperature and voltage were 25 degrees C and 30 kV, respectively. The analytical wavelength was set at 210 nm. Under optimized conditions it is possible to determine DOX in human serum, urine, semen, tears and saliva with recovery of 97.5% (RSD 2.5%). The method was shown to be sensitive (LOD is 1 microg/L) and precise (intra-day RSD 0.2 and 2.4%; inter-days 0.4 and 3.5% for migration time and peak area, respectively). Results for developed SPE-LVSS-MEKC were compared with LVSS-MEKC method with direct sample injection. The new LVSS-MEKC method is presented as a useful technique for rapid determination without extraction procedure of DOX in human urine and serum, using 80 mM of SDS, 10% v/v of methanol and 40 mM borate buffer (pH 9.3; 30 s x 50 mbar; 25 degrees C; 30 kV; 350 nm), but not for the other biological fluids, according to lower sensitivity of the method and because of the sample composition.     

Adsorption of alpha amino acids at the water/goethite interface

The adsorption of amino acids onto mineral surfaces plays an important role in a wide range of areas, e.g., low-temperature aqueous geochemistry, bone formation and protein-bone interactions. In this work, the adsorption of three alpha aminoacids (sarcosine, MIDA and EDDA) onto goethite (alpha-FeOOH) was studied as a function of pH and background electrolyte concentration at 25.0 degrees C, and the molecular structures of the surface complexes formed were analyzed by means of ATR-FTIR spectroscopy. The results showed that adsorption of alpha amino acids were strongly dependent on the functionality and structure of the ligands. No adsorption was detected for the zwitterionic sarcosine indicating that simple alpha amino acids without other ionizable and/or functional groups display insignificant affinity for mineral surfaces such as goethite. With respect to the more complex amino acids, which are surface reactive, the number and relative positions of carboxylate and amine groups determine the types of surface interactions. These interactions range from non-specific outer-sphere to specific inner-sphere interactions as shown by the MIDA and EDDA results, respectively. The results presented herein suggest that isomerically-selective adsorption might only occur for amino acids that are capable of specific surface interactions, either through site-specific hydrogen bonding or inner-sphere complexation.     

Catanionic aggregates formed from drugs and lauric or capric acids enable prolonged release from gels

The aim of this study was to add to the range of charged surfactants that can be used to form catanionic aggregates with oppositely charged surface active drug substances; and to apply these aggregates to prolong drug release from gels. The surfactants used in this study, lauric and capric acids are of natural origin-unlike traditionally used, synthetic, surfactants. The mixtures of drug substances and oppositely charged surfactants were studied visually and with cryogenic transmission electron microscopy. Drug release from gels was studied with a modified USP paddle method. This study shows that lauric and capric acids are as, or even more, active in forming catanionic aggregates than traditionally used surfactants such as sodium dodecyl sulfate. It is shown that the length of the hydrophobic part of the surfactant plays an important role in the formation of pharmaceutically interesting catanionic aggregates. As seen in previous studies, using catanionic vesicles prolongs the drug release from gels and decreases the apparent diffusion coefficient by a factor of 10-50, compared to a gel containing only drug substance.