Characterization of polysorbate 85, a nonionic surfactant,by liquid chromatography vs. ion mobility separation coupled with tandem mass spectrometry

Liquid chromatography (LC) and ion mobility (IM) separation have been coupled with mass spectrometry (MS) and tandem mass spectrometry (MS²) to characterize a commercially important nonionic surfactant, polysorbate 85. The constituents of this amphiphilic blend contained a sorbitan or isosorbide core that was chain extended with poly(ethylene oxide) (PEO) and partially esterified at the PEO termini with oleic acid or, to a lesser extent, other fatty acids. Using interactive LC in reverse-phase mode, the oligomers of the surfactant were separated according to their hydrophobicity/hydrophilicity balance. On the other hand, IM spectrometry dispersed the surfactant oligomers by their charge and collision cross section (i.e. size/shape). With either separation method, an increased number of fatty ester groups and/or lack of the polar sorbitan (or isosorbide) core led to higher retention/drift times, enabling the separation of isobaric species or species with superimposed isotope patterns, so that their ester content could be conclusively identified by MS². LC–MS and IM–MS permitted the detection of several byproducts besides the major PEO-sorbitan oleate oligomers. LC–MS provides the separation resolution needed for quantitative determination of the degree of esterification. IM–MS, which minimizes analysis time and solvent use, is ideally suitable for a fast, qualitative survey of samples differing in their minor constituents or impurities.     

Simultaneous reconstruction of the source term and the surface heat transfer coefficient

We study the problem of identifying unknown source terms in an inverse parabolic problem, when the overspecified (measured) data are given in form of Dirichlet boundary condition u(0,t) = h(t) and , where is an arbitrarily prescribed subregion. The main goal here is to show that the gradient of cost functional can be expressed via the solutions of the direct and corresponding adjoint problems. We prove Hölder continuity of the cost functional and derive the Lipschitz constant in the explicit form via the given data. On the basis of the obtained results, we propose a monotone iteration process. Copyright © 2014 John Wiley & Sons, Ltd.     

Preparation of aluminum-doped zinc oxide (AZO) nano particles by hydrothermal synthesis

Aluminum doped zinc oxide (AZO) nanometric particles were synthesized by hydrothermal method. Aluminum nitrate hydrate, aluminum sec-butoxide and zinc nitrate hydrate were used as the starting materials, and n-propanol and 2-butanol were used as solvents. Ratio of Al₂O₃ in ZnO was kept at 10 wt%. Reaction was conducted in a Teflon autoclave at 175–225 °C for 5 h. Ratios of alcohol, H₂O and HCl to zinc nitrate hydrate were altered and 6 different sets of parameters were investigated. Obtained products were subjected to powder-XRD, particle size measurement, TEM examination and AAS analysis. Single phase AZO particles were obtained at alcohol to zinc nitrate ratio of 35, acid to zinc nitrate ratio of 0.2, at 225 °C. Particle size was determined as 3.2 ± 0.4 nm from TEM examinations and as 1–2 nm from dynamic light scattering. Synthesized particles have amphiphilic character, thus they can be dispersed in both polar and non-polar media. It was seen from the UV-diffuse reflectance spectra that the AZO powder had low reflectance in the UV region and high reflectance in the visible region. The obtained powder has the potential to be utilized in the form of thin films for optical and electronic purposes.     

Streptavidin Modified Carbon Nanotube Based Graphite Electrode for Label‐Free Sequence Specific DNA Detection

Disposable graphite pencil electrodes (PGE) modified with multiwalled carbon nanotubes (MWCNTs)‐streptavidin (STR) conjugates were used for electrochemical monitoring of label‐free DNA hybridization. The surface morphology of PGE electrode before and after hybridization was characterized by scanning electron microscopy. Electrochemical impedance spectroscopy was used to monitor each step of the construction of the DNA biosensor. The biosensor was demonstrated to have excellent selectivity, being able to differentiate complementary sequences from a noncomplementary ones and in addition select the target sequence of DNA from a mixture of other DNA without loss in current sensitivity.     

Polynomial Basis Multiplication over GF(2 m )

In this paper, we describe, analyze and compare various multipliers. Particularly, we investigate the standard modular multiplication, the Montgomery multiplication, and the matrix–vector multiplication techniques.     

A computational study on the amine-oxidation mechanism of monoamine oxidase: insight into the polar nucleophilic mechanism

The proposed polar nucleophilic mechanism of MAO was investigated using quantum chemical calculations employing the semi-empirical PM3 method. In order to mimic the reaction at the enzyme's active site, the reactions between the flavin and the p-substituted benzylamine substrate analogs were modeled. Activation energies and rate constants of all the reactions were calculated and compared with the published experimental data. The results showed that electron-withdrawing groups at the para position of benzylamine increase the reaction rate. A good correlation between the log of the calculated rate constants and the electronic parameter (sigma) of the substituent was obtained. These results agree with the previous kinetic experiments on the effect of p-substituents on the reduction of MAO-A by benzylamine analogs. In addition, the calculated rate constants showed a correlation with the rate of reduction of the flavin in MAO-A. In order to verify the results obtained from the PM3 method single-point B3LYP/6-31G*//PM3 calculations were performed. These results demonstrated a strong reduction in the activation energy for the reaction of benzylamine derivatives having electron-withdrawing substituents, which is in agreement with the PM3 calculations and the previous experimental QSAR study. PM3 and B3LYP/6-31G* energy surfaces were obtained for the overall reaction of benzylamine with flavin. Results suggest that PM3 is a reasonable method for studying this kind of reaction. These theoretical findings support the proposed polar nucleophilic mechanism for MAO-A.     

Reaction of difluoronitroacetyl fluoride with ketones

Conclusions A method was developed for the preparation of -diketones that contain the CF₂NO₂ grouping.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2350–2351, October, 1973.     

Cyclopropanation of 3-(2-Oxo-2<Emphasis Type="Italic">H</Emphasis>-chromen-3-yl-carbonyl)-2<Emphasis Type="Italic">H</Emphasis>-chromen-2-one with Zinc Enolates Derived from 1-Aryl-2,2-dibromoalkanones

Zinc enolates derived from 1-aryl-2,2-dibromoalkanones react with 3-(2-oxo-2H-chromen-3-ylcarbonyl)-2H-chromen-2-one to give 1-alkyl-1-aroyl-1a-(2-oxo-2H-chromen-3-ylcarbonyl)-1a, 7b-dihydrocyclopropa[c]-chromen-2(1H)-ones as a single stereoisomer.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 131–133.Original Russian Text Copyright © 2005 by Shchepin, Russkikh, Uzun, Silaichev.     

Thermodynamics of Pb2+ and Ni2+ adsorption onto natural bentonite from aqueous solutions

Removal of Pb2+ and Ni2+ from aqueous solutions by sorption onto natural bentonite was investigated. Experiments were carried out as a function of particle size, the amount of bentonite, pH, concentration of metals, contact time, and temperature. The adsorption patterns of metal ions onto followed the Langmuir, Freundlich, and Dubinin-Radushkevich isotherms. This included adsorption isotherms of single-metal solutions at 303 K by batch experiments. The thermodynamic parameters (DeltaH,DeltaS,DeltaG) for Pb2+ and Ni2+ sorption onto bentonite were also determined from the temperature dependence. The adsorptions were endothermic reactions. The results suggested that natural bentonite is suitable as a sorbent material for recovery and adsorption of metal ions from aqueous solutions.     

Recognition-mediated assembly of nanoparticles into micellar structures with diblock copolymers

Polystyrene-based diblock copolymers, featuring diaminotriazine functionality on one of the blocks were used to assemble complementary uracil-functionalized nanoparticles into micellar aggregates. The size of these self-assembled aggregates was controlled by block length, as determined in solution (using dynamic light scattering), and in thin films (using transmission electron microscopy).