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981.
Study of immobilized metal affinity chromatography sorbents for the analysis of peptides by on‐line solid‐phase extraction capillary electrophoresis‐mass spectrometry 下载免费PDF全文
Lorena Ortiz‐Martin Fernando Benavente Silvia Medina‐Casanellas Estela Giménez Victoria Sanz‐Nebot 《Electrophoresis》2015,36(6):962-970
Several commercial immobilized metal affinity chromatography sorbents were evaluated in this study for the analysis of two small peptide fragments of the amyloid β‐protein (Aβ) (Aβ(1–15) and Aβ(10–20) peptides) by on‐line immobilized metal affinity SPE‐CE (IMA‐SPE‐CE). The performance of a nickel metal ion (Ni(II)) sorbent based on nitrilotriacetic acid as a chelating agent was significantly better than two copper metal ion (Cu(II)) sorbents based on iminodiacetic acid. A BGE of 25 mM phosphate (pH 7.4) and an eluent of 50 mM imidazole (in BGE) yielded a 25‐fold and 5‐fold decrease in the LODs by IMA‐SPE‐CE‐UV for Aβ(1–15) and Aβ(10–20) peptides (0.1 and 0.5 μg/mL, respectively) with regard to CE‐UV (2.5 μg/mL for both peptides). The phosphate BGE was also used in IMA‐SPE‐CE‐MS, but the eluent needed to be substituted by a 0.5% HAc v/v solution. Under optimum preconcentration and detection conditions, reproducibility of peak areas and migration times was acceptable (23.2 and 12.0%RSD, respectively). The method was more sensitive for Aβ(10–20) peptide, which could be detected until 0.25 μg/mL. Linearity for Aβ(10–20) peptide was good in a narrow concentration range (0.25–2.5 μg/mL, R2 = 0.93). Lastly, the potential of the optimized Ni(II)‐IMA‐SPE‐CE‐MS method for the analysis of amyloid peptides in biological fluids was evaluated by analyzing spiked plasma and serum samples. 相似文献
982.
Salcedo E de Oliveira AB Barraz NM Chakravarty C Barbosa MC 《The Journal of chemical physics》2011,135(4):044517
Molecular dynamics simulations are used to examine the relationship between water-like anomalies and the liquid-liquid critical point in a family of model fluids with multi-Gaussian, core-softened pair interactions. The core-softened pair interactions have two length scales, such that the longer length scale associated with a shallow, attractive well is kept constant while the shorter length scale associated with the repulsive shoulder is varied from an inflection point to a minimum of progressively increasing depth. The maximum depth of the shoulder well is chosen so that the resulting potential reproduces the oxygen-oxygen radial distribution function of the ST4 model of water. As the shoulder well depth increases, the pressure required to form the high density liquid decreases and the temperature up to which the high-density liquid is stable increases, resulting in the shift of the liquid-liquid critical point to much lower pressures and higher temperatures. To understand the entropic effects associated with the changes in the interaction potential, the pair correlation entropy is computed to show that the excess entropy anomaly diminishes when the shoulder well depth increases. Excess entropy scaling of diffusivity in this class of fluids is demonstrated, showing that decreasing strength of the excess entropy anomaly with increasing shoulder depth results in the progressive loss of water-like thermodynamic, structural and transport anomalies. Instantaneous normal mode analysis was used to index the overall curvature distribution of the fluid and the fraction of imaginary frequency modes was shown to correlate well with the anomalous behavior of the diffusivity and the pair correlation entropy. The results suggest in the case of core-softened potentials, in addition to the presence of two length scales, energetic, and entropic effects associated with local minima and curvatures of the pair interaction play an important role in determining the presence of water-like anomalies and the liquid-liquid phase transition. 相似文献
983.
Torres CV Domínguez MJ Carbonari JL Sabini MC Sabini LI Zanon SM 《Natural product communications》2011,6(7):993-994
Baccharis articulata is native of América and traditionally used for the treatment of digestive disorders and urinary infections. Cytotoxicity of aqueous extracts of B. articulata was investigated in Vero cells. As the maximal non cytotoxic concentration has been established, this concentration has been used to evaluate antiviral and virucidal activities against Herpes suis virus type 1, member of the same subfamily of Herpes simplex virus. Aqueous extracts of B. articulata exhibited more than 95% of virucidal activity. These findings support their potential application as a disinfectant or antiseptic with low toxicity and provide a valuable knowledge to ethnopharmacology properties of Baccharis articulata. 相似文献
984.
Freund C Porzio W Giovanella U Vignali F Pasini M Destri S Mech A Di Pietro S Di Bari L Mineo P 《Inorganic chemistry》2011,50(12):5417-5429
The synthesis and the molecular and photophysical characterization, together with solid state and solution structure analysis, of a series of europium complexes based on β-diketonate ligands are reported. The Eu(III) complex emission, specifically its photoluminescence quantum yield (PL-QY), can be tuned by changing ligands which finely modifies the environment of the metal ion. Steady-state and time-resolved emission spectroscopy and overall PL-QY measurements are reported and related to geometrical features observed in crystal structures of some selected compounds. Moreover, paramagnetic NMR, based on the analogous complexes with other lanthanides, are use to demonstrate that there is a significant structural reorganization upon dissolution, which justifies the observed differences in the emission properties between solid and solution states. The energy of the triplet levels of the ligands and the occurrence of nonradiative deactivation processes clearly account for the luminescence efficiencies of the complexes in the series. 相似文献
985.
NMR is a powerful yet intrinsically insensitive technique. The applicability of NMR to chemical and biological systems would be substantially extended by new approaches going beyond current signal-to-noise capabilities. Here, we exploit the large enhancements arising from (13)C photochemically induced dynamic nuclear polarization ((13)C photo-CIDNP) in solution to improve biomolecular NMR sensitivity in the context of heteronuclear correlation spectroscopy. The (13)C-PRINT pulse sequence presented here involves an initial (13)C nuclear spin polarization via photo-CIDNP followed by conversion to anti-phase coherence and transfer to (1)H for detection. We observe substantial enhancements, up to ?200-fold, relative to the dark (laser off) experiment. Resonances of both side-chain and backbone CH pairs are enhanced for the three aromatic residues Trp, His, and Tyr, the σ(32) peptide, and the drkN SH3 protein. The sensitivity of this experiment, defined as signal-to-noise per square root of unit time (S/N)(t), is unprecedented in the NMR polarization enhancement literature dealing with polypeptides in solution. Up to a 16-fold larger (S/N)(t) than for the (1)H-(13)C SE-HSQC reference sequence is achieved, for the σ(32) peptide. Data collection time is reduced up to 256-fold, highlighting the advantages of (1)H-detected (13)C photo-CIDNP in solution NMR. 相似文献
986.
Removal of sulfonamide antibiotics upon conventional activated sludge and advanced membrane bioreactor treatment 总被引:1,自引:0,他引:1
García Galán MJ Díaz-Cruz MS Barceló D 《Analytical and bioanalytical chemistry》2012,404(5):1505-1515
This work reports the removal efficiencies of nine sulfonamides (SAs) and one of their acetylated metabolites during conventional activated sludge (CAS) and membrane bioreactor (MBR) treatments. Two different types of membranes were studied, hollow-fiber membranes and flat-sheet membranes, in two separate pilot plants operating in parallel to a full-scale CAS treatment. A total of 48 water samples and 16 sewage sludge samples were analyzed by liquid chromatography-tandem mass spectrometry. We obtained 100% elimination in the MBR effluents for three SAs (sulfadiazine, sulfadimethoxine, and sulfamethoxypyridazine) and the metabolite. For the rest of the SAs, the removal efficiencies during CAS and MBR treatments were similar and usually below 55%. Sulfamethizole was the most recalcitrant SA, exhibiting negative removal efficiencies in all the treatments investigated. The concentrations of SAs in the different sewage sludge types were also calculated and ranged from 0.01 to 11 ng g(-1). Furthermore, adsorption and biodegradation of SAs in activated sludge were investigated in two sets of batch reactors, which were spiked at high and low concentration (1,000 and 50 ng mL(-1), respectively). All SAs followed a similar trend and, with the exception of sulfathiazole, were not fully eliminated after 25 days of treatment. 相似文献
987.
Michieletti M Bracci A Compostella F De Libero G Mori L Fallarini S Lombardi G Panza L 《The Journal of organic chemistry》2008,73(22):9192-9195
A new practical synthesis of alpha-GalCer and of its analogues is presented, opening the chance to easily modify the sphingosine chain. The common precursor is a disaccharide, obtained by coupling tetra-O-benzyl-D-galactose with allyl 2,3-O-isopropylidene-D-lyxofuranoside. Introduction of alkyl chains via Wittig reaction (for alpha-GalCer and OCH) or via Williamson reaction (for oxa analogues) followed by standard synthetic steps allows one to efficiently obtain such compounds. The analogues are able to activate iNKT cells when presented by CD1d expressing cells. 相似文献
988.
A. Gonçalves C. Costa S. Pereira N. Correia M. M. Silva P. C. Barbosa L. C. Rodrigues I. Henriques R. Martins E. Fortunato 《先进技术聚合物》2012,23(4):791-795
This paper reports the application of a polymethacrylate hydroxyethylene resin based electrolyte in electrochromic (EC) devices. The electrolyte is characterized by electrochemical impedance spectroscopy, visible spectroscopy, TGA, DSC, and DRX and tested as an ionic conductor in an EC device with the following configuration: Substrate/IZO/WO3/Polymer Electrolyte/(CeO2)TiO2/IZO/Substrate. The electrolyte presents an ionic conductivity of 10?7 S/cm at room temperature and TGA analysis show that electrolyte is thermally degraded at 200°C. The EC device based on this polymethacrylate hydroxyethylene resin electrolyte system shows memory effect and exhibits an excellent optical density. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
989.
Carlotto S Polimeno A Ferrante C Benzi C Barone V 《The journal of physical chemistry. B》2008,112(27):8106-8113
A stochastic model for the interpretation of the emission fluorescence of 4-( N, N-dimethylamino)benzonitrile (DMABN) is discussed. We proceed by reviewing the stochastic modeling approach ( Polimeno, A. ; Barbon, A. ; Nordio, P. L. ; Rettig, W. J. Phys. Chem. 1994, 98, 12158 ), in which internal degrees of freedom are coupled with an effective solvent relaxation variable. Potential energy surfaces are obtained using a reliable but computationally cost-effective quantum mechanical (QM) approach, and estimates of dissipative parameters are calculated on the basis of direct hydrodynamic arguments. Emission fluorescence is estimated by solving numerically a diffusion/sink/source equation for the stationary population of excited state and compared to emission fluorescence of DMABN measured experimentally. 相似文献
990.
Manuela Romas Anna Igual Munoz Daniel Mareci Carlos Valero Vidal Silvia Curteanu Daniel Sutiman 《Chemical Papers》2014,68(8):1066-1078
The inhibitory activity of caffeine (1,3,7-trimethyl xanthine) on artificial saliva was studied on a CoCrMo alloy using different electrochemical methods: open circuit potential (OCP), potentiodynamic measurements and electrochemical impedance spectroscopy (EIS). The results show that caffeine produces an inhibitory effect on the anodic currents due to its adsorption on the surface of the alloy. Temperature is another parameter with an influence on corrosion processes, so thermodynamic data were obtained from Arrhenius plots and Langmuir adsorption isotherms. The protective action of caffeine is enhanced at high temperatures at OCP, while for potentiodynamic experiments high temperatures block the inhibitory activity of caffeine and the corrosion rate increases. The process may also be studied by a simulation, determining the functional dependence between OCP, corrosion current density (i corr), corrosion potential (E corr), breakdown potential (E bd) and temperature and amount of caffeine in artificial saliva, for Heraenium® CE. The neural network-based methodology applied in this work provides accurate results, thus proving to be an efficient modelling technique. 相似文献