Coupling capillary electrochromatography with mass spectrometry by using a liquid-junction nano-spray interface

Capillary electrochromatography (CEC) was coupled with mass spectrometry (MS) for the separation of some selected pesticides and drug enantiomers. CEC separations were carried out in fused silica capillaries packed with either 5 μm RP₁₈ silica or 5 μm silica modified vancomycin particles. The capillary column was connected with the MS utilizing a laboratory-made liquid-junction interface equipped with a 50 μm I.D. capillary-tip positioned at a few mm from the orifice of the MS. The CEC–MS set-up was operated without external pressure assistance during the electrochromatographic run commonly used to avoid bubble formation. However a hydrostatic pressure of a few kPa was applied only to the liquid-junction interface to optimize the ion-spray due to the low I.D. of the capillary-tip. In order to optimize the CEC–MS method, several experimental parameters were studied, namely the inlet pressure, the hydrostatic pressure into the liquid-junction interface, the type of sheath-liquid and the mobile phase. The application of an inlet pressure influenced only analyte retention times that were shortened by increasing the pressure. On the contrary the hydrostatic pressure applied to the interface increased the flow rate into the tip also increasing the ion-signal recorded in the mass spectrometry. The ion-signal raised almost linearly by increasing the outlet pressure till 3.5 kPa and then decreased. The separation of the selected pesticides was not influenced at all changing the hydrostatic pressure on the interface. Some basic enantiomeric compounds of pharmaceutical interest were successfully separated by CEC achieving good resolution. They were detected by MS with limit of detection in a range of 0.24–0.60 μg/mL.     

Iron–cobalt nanocrystalline alloy supported on a cubic mesostructured silica matrix: FeCo/SBA-16 porous nanocomposites

A series of novel nanocomposites constituted of FeCo nanoparticles dispersed in an ordered cubic Im3m mesoporous silica matrix (SBA-16) have been successfully synthesized using the wet impregnation method. SBA-16, prepared using the non-ionic Pluronic 127 triblock copolymer as a structure-directing agent, is an excellent support for catalytic nanoparticles because of its peculiar three-dimensional cage-like structure, high surface area, thick walls, and high thermal stability. Low-angle X-ray diffraction, N₂ physisorption, and transmission electron microscopy analyses show that after metal loading, calcination at 500 °C, and reduction in H₂ flux at 800 °C, the nanocomposites retain the well-ordered structure of the matrix with cubic symmetry of pores. FeCo alloy nanoparticles with spherical shape and narrow size distribution (4–8 nm) are homogeneoulsy distributed throughout the matrix and they seem in a large extent to be allocated inside the pores.     

Perturbed asymptotically linear problems

The aim of this paper is to investigate the existence of solutions of the semilinear elliptic problem $$\left\{\begin{array}{ll} -\Delta u\ =\ p(x, u) + \varepsilon g(x, u)\quad {\rm in}\,\, \Omega, \\ u=0 \quad\quad\quad\quad\quad\quad\quad\quad\quad\,\,\,\,\,\,{\rm on}\,\, \partial\Omega, \end{array} \right. \quad\quad\quad(0.1) $$ where Ω is an open bounded domain of ${\mathbb{R}^N}$ , ${\varepsilon\in\mathbb{R}, p}$ is subcritical and asymptotically linear at infinity, and g is just a continuous function. Even when this problem has not a variational structure on ${H^1_0(\Omega)}$ , suitable procedures and estimates allow us to prove that the number of distinct critical levels of the functional associated to the unperturbed problem is “stable” under small perturbations, in particular obtaining multiplicity results if p is odd, both in the non-resonant and in the resonant case.     

Viscosity Characterization of the Value Function of an Investment-Consumption Problem in Presence of an Illiquid Asset

We study a problem of optimal investment/consumption over an infinite horizon in a market consisting of a liquid and an illiquid asset. The liquid asset is observed and can be traded continuously, while the illiquid one can only be traded and observed at discrete random times corresponding to the jumps of a Poisson process. The problem is a nonstandard mixed discrete/continuous optimal control problem, which we face by the dynamic programming approach. The main goal of the paper is the characterization of the value function as unique viscosity solution of an associated Hamilton–Jacobi–Bellman equation. We then use such a result to build a numerical algorithm, allowing one to approximate the value function and so to measure the cost of illiquidity.     

A class of piecewise interpolating functions based on barycentric coordinates

Piecewise interpolation methods, as spline or Hermite cubic interpolation methods, define the interpolant function by means of polynomial pieces and ensure that some regularity conditions are guaranteed at the break-points. In this work, we propose a novel class of piecewise interpolating functions whose expression depends on the barycentric coordinates and a suitable weight function. The underlying idea is to specialize to the 1D settings some aspects of techniques widely used in multi-dimensional interpolation, namely Shepard’s, barycentric and triangle-based blending methods. We show the properties of convergence for the interpolating functions and discuss how, in some cases, the properties of regularity that characterize the weight function are reflected on the interpolant function. Numerical experiments, applied to some case studies and real scenarios, show the benefit of our method compared to other interpolant models.     

Synthesis and characterization of sulfonated copolyethersulfones

The present article deals with the synthesis and characterization of some sulfonated copolyethersulfones. The synthetic approach differs from the post sulfonation approach traditionally reported in the literature. The synthetic procedure is based on the use of sulfonated monomers which are then reacted with previously synthesized telechelic hydoxy‐ended poly (ether sulpnone)s. Combining the MALDI‐TOF MS and ¹H NMR analyses, with SEC‐Viscometry and TGA measurements, we demonstrate a powerful tool for characterizing the chemical composition, end chains, degree of sulfonation (DS) and molecular mass distribution (MMD) of disulfonated poly(arylene ether‐sulfone) copolymers. The characterization techniques allowed to determine the exact nature of the copolymers synthesized and to reveal some interesting features about the reaction. DMA data show that the glass transition temperature of sulfonated copolymers with similar DS increase as raise their MMD. Copolymers with a DS of 10–11 mol % reach a T_g of 244–246 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3010–3023, 2010     

Racemization at C-2 of naringin in pummelo (Citrus grandis) with increasing maturity determined by chiral high-performance liquid chromatography

The relative content of (2S)- and (2R)-naringin in the albedo of pummelo during maturation in the entire season was determined by normal-phase HPLC using Chiralpak IB, a polysaccharide-derived chiral stationary phase, and n-hexane/ethanol doped with 0.5% TFA as mobile phase. A sigmoid curve was obtained showing variation from 95.3% of (2S)-naringin in very immature fruits to 53% in mature fruit samples (2.3 and 14.4 cm diameter, respectively). A comparison was made with previous results obtained for grapefruit and sour orange and a tentative explanation of the bitter taste of sour orange is proposed. The Chiralpak IB is much more efficient with respect to the Chiralcel OD used for the other two Citrus species and separation and resolution factors of 1.73 and 9.2, respectively, were achieved. Authentic samples of naringin and neohesperidin were also separated into their C-2 diastereomers with Chiralpak IB and isolation of the pure diastereomers of naringin was accomplished.     

Determination of elemental compositions by gas chromatography/time‐of‐flight mass spectrometry using chemical and electron ionization

Many metabolomic applications use gas chromatography/mass spectrometry (GC/MS) under standard 70 eV electron ionization (EI) parameters. However, the abundance of molecular ions is often extremely low, impeding the calculation of elemental compositions for the identification of unknown compounds. On changing the beam‐steering voltage of the ion source, the relative abundances of molecular ions at 70 eV EI were increased up to ten‐fold for alkanes, fatty acid methyl esters and trimethylsilylated metabolites, concomitant with 2‐fold absolute increases in ion intensities. We have compared the abundance, mass accuracy and isotope ratio accuracy of molecular species in EI with those in chemical ionization (CI) with methane as reagent gas under high‐mass tuning. Thirty‐three peaks of a diverse set of trimethylsilylated metabolites were analyzed in triplicate, resulting in 342 ion species ([M+H]⁺, [M–CH₃]⁺ for CI and [M]^{+ .} , [M–CH₃]^{+ .} for EI). On average, CI yielded 8‐fold more intense molecular species than EI. Using internal recalibration, average mass errors of 1.8 ± 1.6 mm/z units and isotope ratio errors of 2.3 ± 2.0% (A+1/A ratio) and 1.7 ± 1.8% (A+2/A ratio) were obtained. When constraining lists of calculated elemental compositions by chemical and heuristic rules using the Seven Golden Rules algorithm and PubChem queries, the correct formula was retrieved as top hit in 60% of the cases and within the top‐3 hits in 80% of the cases. Copyright © 2010 John Wiley & Sons, Ltd.     

Localization of Bose-Einstein condensates in optical lattices

The dynamics of repulsive bosons condensed in an optical lattice is effectively described by the Bose-Hubbard model. The classical limit of this model, reproduces the dynamics of Bose-Einstein condensates, in a periodic potential, and in the superfluid regime. Such dynamics is governed by a discrete nonlinear Schrödinger equation. Several papers, addressing the study of the discrete nonlinear Schrödinger dynamics, have predicted the spontaneous generation of (classical) breathers in coupled condensates. In the present contribute, we shall focus on localized solutions (quantum breathers) of the full Bose-Hubbard model. We will show that solutions exponentially localized in space and periodic in time exist also in absence of randomness. Thus, this kind of states, reproduce a novel quantum localization phenomenon due to the interplay between bounded energy spectrum and non-linearity.