Heteroscedastic controlled calibration model applied to analytical chemistry

In chemical analyses performed by laboratories, one faces the problem of determining the concentration of a chemical element in a sample. In practice, one deals with the problem using the so‐called linear calibration model, which considers that the errors associated with the independent variables are negligible compared with the former variable. In this work, a new linear calibration model is proposed assuming that the independent variables are subject to heteroscedastic measurement errors. A simulation study is carried out in order to verify some properties of the estimators derived for the new model and it is also considered the usual calibration model to compare it with the new approach. Three applications are considered to verify the performance of the new approach. Copyright © 2010 John Wiley & Sons, Ltd.     

Theoretical infrared line shapes of H‐bonds within the strong anharmonic coupling theory and Fermi resonances effects

In this article, we extend a previous work toward presenting a theoretical study of the effects of Fermi resonances and the fundamental anharmonic coupling parameter α between the high‐frequency mode and the H‐bond bridge. The model incorporates (i) both intrinsic anharmonicities of the fast mode (double well potential) and the H‐bond Bridge (Morse potential), (ii) strong anharmonic coupling theory, (iii) Fermi resonances by the aid of an anharmonic coupling between the fast mode and one or several harmonic bending modes, (iv) quadratic modulation of both the angular frequency and the equilibrium position of the X? …Y stretching mode on the intermonomer ? H… motions, and (v) the quantum direct (fast and bending modes) and indirect dampings (slow mode). The IR spectral density is obtained by Fourier transform of the autocorrelation function of the transition dipole moment operator of the X? H bond. The numerical calculation shows that Fermi resonances generate very complicated profiles with multisubstructure and also provide a direct evidence of Fermi resonances which were predicted to be a major feature of H‐bonds. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Determination of aristolochic acid in urine using hollow fiber liquid-phase microextraction combined with high-performance liquid chromatography

A simple and efficient hollow fiber liquid‐phase microextraction (HF‐LPME) technique in conjunction with high‐performance liquid chromatography is presented for extraction and quantitative determination of aristolochic acid I in human urine samples. Several parameters influencing the efficiency of HF‐LPME were investigated and optimized, including extraction solvent, stirring rate, extraction time, pH of donor phase and acceptor phase. Excellent sample clean‐up was observed and good linearity with coefficient of 0.9999 was obtained in the range of 15.4–960 µg/L. This method provided a 230‐fold enrichment factor and good repeatability with relative standard deviations (RSD) lower than 6.0%. The limit of detection value for the analyte in urine sample was 0.01 µg/L at a signal‐to‐noise ratio of 3. The extraction recovery from urine samples was 61.8% with an RSD of 9.71%. Copyright © 2010 John Wiley & Sons, Ltd.     

Optimal paths for a light-driven engine with a linear phenomenological heat transfer law

An irreversible light-driven engine is described in this paper, in which the heat transfer between the working fluid and the environment obeys a linear phenomenological heat transfer law [ q ∝Δ(T -1)], with a working fluid composed of the bimolecular reacting system 2SO 3 F■S 2 O 6 F2. Piston trajectories maximizing work output and minimizing entropy generation are determined for such an engine with rate-dependent loss mechanisms of friction and heat leakage. The optimal control theory is applied to determi...     

Investigation of the pyrolysis products of methionine-enkephalin-Arg-Gly-Leu using liquid chromatography-tandem mass spectrometry

Low-temperature pyrolysis of methionine-enkephalin-Arg-Gly-Leu has been carried out and the non-volatile residues have been analyzed. The fragments were separated and characterized by LC-UV/Vis-MS/MS. Two major types of pyrolysis products were identified by matching the experimental results with a theoretical list that contains the expected fragments. These products were mainly composed of cyclic oligopeptides and linear fragments produced from the peptide backbone. These fragments have preserved the sequence of amino acids in the peptide. In some cases, a complete or partial loss of an amino-acid side group was observed. Tandem mass spectrometry and cyanogen bromide cleavage experiments were used to confirm the nature of the cyclic and linear pyrolysates, in addition to chromatographic and mass spectrometric data of actual standard synthetic cyclic peptides.     

Mass spectrometry of fluorocarbon‐labeled glycosphingolipids

A method for generation of novel fluorocarbon derivatives of glycosphingolipids (GSLs) with high affinity for fluorocarbon phases has been developed, and their potential applications to mass spectrometry (MS)‐based methodologies for glycosphingolipidomics have been investigated. Sphingolipid ceramide N‐deacylase (SCDase) is used to remove the fatty acid from the ceramide moiety, after which a fluorocarbon‐rich substituent (F‐Tag) is incorporated at the free amine of the sphingoid. In initial trials, a neutral GSL, globotriaosylceramide (Gb₃Cer), three purified bovine brain gangliosides, and four fungal glycosylinositol phosphorylceramides (GIPCs) were de‐N‐acylated, derivatized by prototype F‐Tags, and recovered by solid phase extraction on fluorocarbon‐derivatized silica (F‐SPE). The efficacy of SCDase treatment of GIPCs was here demonstrated for the first time. Compatibility with subsequent per‐N,O‐methylation was established for the F‐tagged Gb₃ Cer and purified gangliosides, and extensive mass spectra (MS¹ and MS²) consistent with all of the expected products were acquired. The potential use of F‐tagged derivatives for a comprehensive MS based profiling application was then demonstrated on a crude ganglioside mixture extracted from bovine brain. Finally, a simple trial in microarray format demonstrated fixation of F‐tagged G_M1 ganglioside to a fluorous glass surface, with the glycan intact and available for interaction with a fluorescent derivative of cholera toxin B chain. The methods described thus provide a new avenue for rapid GSL recovery or cleanup, potentially compatible with a variety of platforms for mass spectrometric profiling and structure analysis, as well as parallel analysis of functional interactions. Copyright © 2010 John Wiley & Sons, Ltd.     

Wavelet formulation of the polarizable continuum model

The first implementation of a wavelet discretization of the Integral Equation Formalism (IEF) for the Polarizable Continuum Model (PCM) is presented here. The method is based on the application of a general purpose wavelet solver on the cavity boundary to solve the integral equations of the IEF‐PCM problem. Wavelet methods provide attractive properties for the solution of the electrostatic problem at the cavity boundary: the system matrix is highly sparse and iterative solution schemes can be applied efficiently; the accuracy of the solver can be increased systematically and arbitrarily; for a given system, discretization error accuracy is achieved at a computational expense that scales linearly with the number of unknowns. The scaling of the computational time with the number of atoms N is formally quadratic but a N^1.5 scaling has been observed in practice. The current bottleneck is the evaluation of the potential integrals at the cavity boundary which scales linearly with the system size. To reduce this overhead, interpolation of the potential integrals on the cavity surface has been successfully used. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Hydrogen Production by Water Dissociation in Surface‐Modified BaCoxFeyZr1−x−yO3−δ Hollow‐Fiber Membrane Reactor with Improved Oxygen Permeation

A porous perovskite BaCo_xFe_yZr_0.9?x?yPd_0.1O_3?δ (BCFZ‐Pd) coating was deposited onto the outer surface of a BaCo_xFe_yZr_1?x?yO_3?δ (BCFZ) perovskite hollow‐fiber membrane. The surface morphology of the modified BCFZ fiber was characterized by scanning electron microscopy (SEM), indicating the formation of a BCFZ‐Pd porous layer on the outer surface of a dense BCFZ hollow‐fiber membrane. The oxygen permeation flux of the BCFZ membrane with a BCFZ‐Pd porous layer increased 3.5 times more than that of the blank BCFZ membrane when feeding reactive CH₄ onto the permeation side of the membrane. The blank BCFZ membrane and surface‐modified BCFZ membrane were used as reactors to shift the equilibrium of thermal water dissociation for hydrogen production because they allow the selective removal of the produced oxygen from the water dissociation system. It was found that the hydrogen production rate increased from 0.7 to 2.1 mL H₂ min^?1 cm^?2 at 950 °C after depositing a BCFZ‐Pd porous layer onto the BCFZ membrane.