Potential of prodendronic polyamines with modulated segmental charge density as novel coating for fast and efficient analysis of peptides and basic proteins by CE and CE‐MS

In this work, the suitability of a new polymer family has been investigated as capillary coatings for the analysis of peptides and basic proteins by CE. This polymer family has been designed to minimize or completely prevent protein–capillary wall interactions and to modify the EOF. These coating materials are linear polymeric chains bearing as side cationizable moiety a dentronic triamine derived from N,N,N’,N’‐tetraethyldiethylenetriamine (TEDETA), which is linked to the backbone through a spacer (unit labeled as TEDETAMA). Four different polymers have been prepared and evaluated: a homopolymer which comprised only of those cationizable repetitive units of TEDETAMA, and three copolymers that randomly incorporate TEDETAMA together with neutral hydrosoluble units of N‐(2‐hydroxypropyl) methacrylamide (HPMA) at different molar percentages (25:75, 50:50 and 75:25). It has been demonstrated that the composition of the copolymers influences the EOF and therefore the separation of the investigated biopolymers. Among the novel polymers studied, poly‐(TEDETAMA‐co‐HPMA) 50:50 copolymer was successfully applied as coating material of the inner capillary surface in CE‐UV and CE‐MS, providing EOF reversing together with fast and efficient baseline separation of peptides and basic proteins. Finally, the feasibility of the polymer‐coated capillary was shown through the analysis of lysozyme in a cheese sample.     

Mechanochemical Synthesis of Urea Adducts with Long Chain Alkyl Derivatives

The adducts of urea and solid alkyl derivatives can beobtained mechanochemically in good yields. Theproducts synthesized by grinding the solid reagentshave identical IR spectra and XRD powder patterns tothose obtained by crystallization from ethanolicsolutions.     

Adsorption and separation of light alkane hydrocarbons by porous hexacyanocobaltates (III)

The adsorption and separation of light n‐alkane hydrocarbons (propane, butane, pentane, hexane and heptane) by zinc and cadmium hexacyanocobaltates (III) were studied from inverse gas chromatographic data. These two solids are representative of the porous frameworks found for transition metals hexacyanometallates. For cadmium, the porous framework is related to the presence of systematic vacancies for the building block, [Co(CN)₆], while for Zn it is a consequence of a tetrahedral coordination for the Zn atom. These linear light hydrocarbons (paraffins) are effectively separated by these two porous frameworks. The involved differential adsorption heats and the related separation coefficients were estimated from the recorded chromatographic data. No significant differences for the separation ability of light n‐alkane hydrocarbons by the evaluated materials were observed. Copyright © 2009 John Wiley & Sons, Ltd.     

Porous framework of T2[Fe(CN)6]·xH2O with T=Co, Ni, Cu, Zn, and H2 storage

The materials under study were prepared from aqueous solutions of ferrocyanic acid and salts of the involved transition metals and their crystal structure solved and refined from X-ray powder diffraction data. Complementary information from thermogravimetric, infrared and Mössbauer data was also used for the structural study. Three different crystal structures were found: hexagonal (P-3) for Zn with the zinc atom coordinated to three N ends of CN groups plus a water molecule, cubic (Pm-3m) for Ni and Cu, and monoclinic (P2₁/m) for Co. For Ni and Cu the obtained solids have an open channel framework related to 50% of vacancies for the building unit, [Fe(CN)₆]. In the as-synthesized material the framework free volume is occupied by coordinated and hydrogen-bonded water molecules. These of hexacyanoferrates (II) have received certain attention as prototype of materials for the hydrogen storage. In the anhydrous phase of Ni and Cu, 50% of the metal (T) coordination sites, located at the cavities surface, will be available to interact with the hydrogen molecule. However, when the crystal waters are removed the porous frameworks collapse as it is suggested by H₂ and CO₂ adsorption data. For Co, a structure of stacked layers was found where the cobalt atoms have both tetrahedral and octahedral coordination. The layers remain together through a network of hydrogen-bonding interactions between coordinated and weakly bonded water molecules. No H₂ adsorption was observed in the anhydrous phase of Co. For Zn, the porous framework remains stable on the water removal but with a system of narrow channels and a small available volume, also inaccessible to H₂.     

A new multiresponse optimization approach in combination with a D-Optimal experimental design for the determination of biogenic amines in fish by HPLC-FLD

A new strategy to approach multiresponse optimization in conjunction to a D-optimal design for simultaneously optimizing a large number of experimental factors is proposed. The procedure is applied to the determination of biogenic amines (histamine, putrescine, cadaverine, tyramine, tryptamine, 2-phenylethylamine, spermine and spermidine) in swordfish by HPLC-FLD after extraction with an acid and subsequent derivatization with dansyl chloride. Firstly, the extraction from a solid matrix and the derivatization of the extract are optimized. Ten experimental factors involved in both stages are studied, seven of them at two levels and the remaining at three levels; the use of a D-optimal design leads to optimize the ten experimental variables, significantly reducing by a factor of 67 the experimental effort needed but guaranteeing the quality of the estimates. A model with 19 coefficients, which includes those corresponding to the main effects and two possible interactions, is fitted to the peak area of each amine. Then, the validated models are used to predict the response (peak area) of the 3456 experiments of the complete factorial design. The variability among peak areas ranges from 13.5 for 2-phenylethylamine to 122.5 for spermine, which shows, to a certain extent, the high and different effect of the pretreatment on the responses. Then the percentiles are calculated from the peak areas of each amine. As the experimental conditions are in conflict, the optimal solution for the multiresponse optimization is chosen from among those which have all the responses greater than a certain percentile for all the amines. The developed procedure reaches decision limits down to 2.5 μg L⁻¹ for cadaverine or 497 μg L⁻¹ for histamine in solvent and 0.07 mg kg⁻¹ and 14.81 mg kg⁻¹ in fish (probability of false positive equal to 0.05), respectively.     

Mössbauer spectroscopic study of Prussian Blue from different provenances

Ferric ferrocyanides synthesized from different sources of ferric cations and ferrocyanide anions and those derived from ferrous ferricyanide, ferrous ferrocyanide and ferric ferricyanide have been studied using Mössbauer and XRD techniques. Structural information of the effect of the provenance on the properties of the final compound is obtained. Significant correlations between isomer shift and quadrupole splitting of inner and outer iron cations have been observed.     

Magnetic hyperfine field distribution in pyrrhotites from Mössbauer spectroscopy

Mössbauer spectra from intermediate pyrrhotite (Fe_1–xS) samples were interpreted according to their hyperfine magnetic field distribution functions at the Fe nuclei in these sulfides. Seven non-equivalent Mössbauer sites for Fe were distinguished by their peak positions in the distribution functions obtained.     

Combinatorial aspects of sequences of point blowing ups

We study morphisms given by composition of a sequence of point blow ups of smoothd-dimensional varieties in terms of combinatorial information coming from thed-ary intersection form on divisors with exceptional support. Some application to the classification of space curve singularities are derived. Supported by D.G.I.C.Y.T. PB91-0210-C02-01     

Mössbauer research of magnetic particles in medicinal ointments

Stability of the properties of magnetite particles in novel medicinal magnetic ointments of multipurpose application was studied using Mössbauer spectroscopy. Comparative analysis of the results obtained by model fitting of⁵⁷Fe nuclei spectra with those known for the system Fe₃O₄-γ-Fe₂O₃ allowed to identify the phase composition of the particles. This composition, as well as that of the initial pure component in the form of a highly dispersed fraction (～100 Å), differs noticeably from the stoichiometric one. Despite their small sizes, the particles exhibit no superparamagnetism (in the temperature range from 95 to 300 K). Radiative sterilization of the ointments has no effect on the magnetic component composition.