Optimization and validation of an LC-fLD method for biotin in infant formula, infant cereals, cocoa-malt beverages, and clinical nutrition products

A fast and simple chromatographic method to determine biotin in foods is presented. Biotin is extracted using papain (60 degrees C, 1 h). After pH adjustment and filtration, biotin is determined by LC with fluorescence detection using postcolumn reagent avidin-FITC (avidin labeled with fluorescein isothiocyanate). The method has been validated in a large range of products: milk- and soy-based infant formulas, cereals, cocoa-malt beverages, and clinical nutrition products. The method showed recovery rates of 98.1 +/- 5.7% (average +/- SD) in a large range of concentrations. Biotin concentrations determined in infant formula standard reference materials 1846 and 1849 were in agreement with reference values. RSD of repeatability (RSDr) varied from 2.0 to 4.5%, and intermediate reproducibility (RSD(iR)) from 5.8 to 9.4%. LOD and LOQ were 3.0 and 5.0 microg/100 g, respectively. The proposed method is suitable for routine analysis of biotin in fortified foods (infant formulas, infant cereals, cocoa-malt beverages, and clinical nutrition products). It can be used as a faster, more selective, and precise alternative to the classical microbiological determination, and is easily transferable among laboratories.     

Apatite type lanthanum silicate and composite anode half cells

Apatite type rare earth silicates are being extensively studied as electrolyte material for intermediate temperature solid oxide fuel cells (SOFC). In this paper we presents results on synthesis of Al and/or Fe-doped ATLS, the design of compatible anode materials, thermal expansion properties and co-sintering of half-cells from expansion matched materials using the advanced pulsed electric current sintering (PECS) technique. The issues related to the co-sintering of half cells have been addressed successfully by the combined use of nano powders and PECS.     

Preparative-Scale Biocatalytic Oxygenation of N-Heterocycles with a Lyophilized Peroxygenase Catalyst

A lyophilized preparation of an unspecific peroxygenase variant from Agrocybe aegerita (rAaeUPO-PaDa-I-H) is a highly effective catalyst for the oxygenation of a diverse range of N-heterocyclic compounds. Scalable biocatalytic oxygenations (27 preparative examples, ca. 100 mg scale) have been developed across a wide range of substrates, including alkyl pyridines, bicyclic N-heterocycles and indoles. H₂O₂ is the only stoichiometric oxidant needed, without auxiliary electron transport proteins, which is key to the practicality of the method. Reaction outcomes can be altered depending on whether hydrogen peroxide was delivered by syringe pump or through in situ generation using an alcohol oxidase from Pichia pastoris (PpAOX) and methanol as a co-substrate. Good synthetic yields (up to 84 %), regioselectivity and enantioselectivity (up to 99 % ee) were observed in some cases, highlighting the promise of UPOs as practical, versatile and scalable oxygenation biocatalysts.     

Solubilization of Nile Red in Micelles and Protomicelles of Sodium Dodecyl Sulfate

A spectrophotometric study of the solubilization and aggregation of the Nile red dye (NR) in premicellar and micellar aqueous solutions of sodium dodecyl sulfate (SDS) was carried out. The experiments were conducted both with saturated solutions of NR under conditions of thermodynamic equilibrium of the solution with a dye precipitate, and at a constant concentration of NR in a homogeneous solution. In the first case, it was proved theoretically and verified experimentally that with an increase in the SDS concentration, the NR concentration always increases, and at the limit of low concentrations, the dependence is linear. In both cases, the concentration of NR dimers as a function passes through a maximum in the premicellar region. There are no dimers in the micellar region. The extinction coefficients of NR monomers in SDS solutions were determined both below and above the critical micelle concentration (CMC) of SDS. A solubilization curve with branches for the premicellar and micellar regions was constructed, the intersection of which was used to find the CMC value in the system under study. The state of deep supersaturation of the NR solution in the metastable state upon dilution of the micellar system with water was studied. It was found that, in addition to dimers, molecular aggregates of higher orders were also formed.     

Separation of water-soluble vitamins by reversed-phase high performance liquid chromatography with ultra-violet detection: application to polyvitaminated premixes

Nine water-soluble vitamins: [thiamine (B1), ascorbic acid (C), nicotinamide (PP), pyridoxine (B6), calcium pantothenate (B5), folic acid (B9), cyanocobalamin (B12), riboflavin (B2) and biotin (B8)] were separated on a YMC-Pack Pro C18 column (250 mm x 4.6 mm, 5 microm particle size) in a single run with a gradient elution of mobile phase consisting of 0.025% trifluoroacetic acid pH 2.6 (solvent A) and acetonitrile (solvent B). The separation was achieved within 17 min with a flow rate of 0.8 ml min(-1) and the detection was performed at two wavelengths (210 and 275 nm). The calibration graphs plotted with six concentrations of each vitamin were linear with a regression coefficient R2 > 0.995. The method was applied for the quantification of vitamins B1, C, PP, B6, B5, B9 B2 and B8 in polyvitaminated premixes (premixes) used for the fortification of infant nutrition products. The sample preparation involves an aqueous extraction of vitamins and two different samples dilution were used prior the LC-analysis. The specificity of the method was demonstrated by the retention characteristics, UV spectra and by comparing the peak purity with the standard of each vitamin. The repeatability of the method was evaluated at different level of concentrations on 12 premixes and the coefficients of variation (CVr) were below 6.5%. The values of the intermediate precision (CV1) were below 9.6% (n = 6). The concentrations of vitamins found in premixes with our method were comparable to the declared values, since no bias was found between the two sets of results at 95% confidence. The simplicity of the procedure should make it highly desirable for quality control of premixes in the food industry.     

Amination of octafluoronaphthalene in liquid ammonia: 2,6- and 2,7-Diaminohexafluoronaphthalenes selective preparation

Monoamination of octafluoronaphthalene by liquid ammonia affords 2-aminoheptafluoronaphthalene mainly (isolated yield 85-90%). Diamination of octafluoronaphthalene or amination of 2-aminoheptafluoronaphthalene affords a mixture of isomeric 1,6-, 1,7-, 2,6-, and 2,7-diaminohexafluoronaphthalenes with considerable prevalence of the 2,7-isomer (∼70%), thus being the first example of the predominant substitution at position 7 in 2-substituted polyfluoronaphthalenes. The 2,7/2,6 ratio of 2-X-heptafluoronaphthalene (X = ⁻NH, NH₂ and NHAc) amination diminishes with the decrease of electron-donating effect of the substituent; 2,7-diaminohexafluoronaphthalene forms in the reactions of 2-aminoheptafluoronaphthalene or octafluoronaphthalene with excess of NaNH₂ in liquid ammonia and 2,6-diaminohexafluoronaphthalene—in the reaction of 2-acetylamidoheptafluoronaphthalene with liquid ammonia followed by acetylamido group hydrolysis. The method of the selective preparation of these diamines based on the reversible transformation of amino group and a convenient technique of their high purity isolation by complexation with crown ether have been elaborated.     

Reactions of 2-phenylpyrrole with bromobenzoylacetylene on metal oxides active surfaces

The solvent-free interaction of 2-phenylpyrrole with bromobenzoylacetylene (room temperature) upon their grinding with solid metal oxides (MgO, CaO, ZnO, BaO, Al₂O₃, TiO₂, ZrO₂) and salts (CaCO₃, ZrSiO₄) leads to either the cross-coupling product or the adduct of pyrrole addition to the riple bond of acetylene. The ethynylation is accompanied by the formation of intermediate and side products: E-2-(1-bromo-2-benzoylethenyl)-5-phenylpyrrole and 1,1-di(5-phenylpyrrol-2-yl)-2-benzoylethene. The activity of the metal oxides in the ethynylation reaction falls in the order (in the brackets, the content of 2-benzoylethynyl-5-phenylpyrrole in the reaction mixture is given): ZnO (81%), BaO (73%), Al₂O₃ (71%), MgO (69%), CaO (50%). The oxides, SiO₂, TiO₂, ZrO₂, and the salts, CaCO₃ and ZrSiO₄, are inactive in the ethynylation reaction affording only the intermediate adduct, with ZrO₂ the isolated yield of the bromoethenylpyrrole reaching 60%. ESR monitoring shows the reaction to start from one electron transfer from pyrrole to acetylene mediated by the oxide surface. The adduct is readily converted on Al₂O₃ to 2-(benzoylethynyl)-5-phenylpyrrole crystallized mostly as cis-rotamer (X-ray data).     

A High‐Quality Professional Development for Teachers of Grades 3–6 for Implementing Engineering into Classrooms

With the increasing emphasis on integrating engineering into K‐12 classrooms to help meet the needs of our complex and multidisciplinary society, there is an urgent need to investigate teachers' engineering‐focused professional development experiences as they relate to teacher learning, implementation, and student achievement. This study addresses this need by examining the effects of a professional development program focused on engineering integration, and how teachers chose to implement engineering in their classrooms as a result of the professional development. 198 teachers in grades 3–6 from 43 schools in 17 districts participated in a yearlong professional development program designed to help integrate the new state science standards, with a focus on engineering, into their teaching. Posters including lesson plans and student artifacts were used to assess teachers' engineering practices and the implementation in their classrooms. Results indicated that the majority of the teachers who participated in the professional development were able to effectively implement engineering design lessons in their classrooms suggesting that the teachers' success in implementing engineering lessons in their classroom was closely related to the structure of the professional development program.     

Reliability of disturbance rejection control based on the geometrical disturbance decoupling

In this note, a reliable disturbance decoupled control system based on the geometrical technique is proposed. For this purpose, first, the conditions for nominal disturbance detection and rejection is introduced by using invariant subspaces. Then, the fragility issue of the controller/observer is addressed with appropriate H_∞ constraints in the form of some linear matrix inequalities (LMIs). In contrast to conventional pole placement method suitable for systems by neglecting sources of uncertainty, in the presented method, the disturbance rejection problem reduces to a quadratic stability problem. It is observed that the proposed method has a better attenuation performance than classical observer-based non-fragile controller. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hyperbolic stefan problem in a curvilinear sector

The problem with unknown boundaries for a first-order semilinear hyperbolic system is studied in the case where the curve of definition of the initial conditions degenerates to a point. An existence and uniqueness theorem for a classical solution of the problem is proved for small t.