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951.
The validation of an analytical procedure means the evaluation of some performance criteria such as accuracy, sensitivity, linear range, capability of detection, selectivity, calibration curve, etc. This implies the use of different statistical methodologies, some of them related with statistical regression techniques, which may be robust or not. The presence of outlier data has a significant effect on the determination of sensitivity, linear range or capability of detection amongst others, when these figures of merit are evaluated with non-robust methodologies.In this paper some of the robust methods used for calibration in analytical chemistry are reviewed: the Huber M-estimator; the Andrews, Tukey and Welsh GM-estimators; the fuzzy estimators; the constrained M-estimators, CM; the least trimmed squares, LTS. The paper also shows that the mathematical properties of the least median squares (LMS) regression can be of great interest in the detection of outlier data in chemical analysis. A comparative analysis is made of the results obtained by applying these regression methods to synthetic and real data. There is also a review of some applications where this robust regression works in a suitable and simple way that proves very useful to secure an objective detection of outliers. The use of a robust regression is recommended in ISO 5725-5. 相似文献
952.
The Schlieren effect is a consequence of light inflexions altering the spectrophotometric measurements that are due to the formation of optical artefacts such as mirror and lenses inside the flowing sample. It may influence signal-to-noise ratio, sample throughput and measurement repeatability in spectrophotometric flow-based procedures. It was critically examined, in order to provide guidelines for system design. Results demonstrate that the magnitude of the Schlieren effect is governed by the combined influence of two components. The first is related to loss of light by reflection at sharp liquid interfaces and prevails under poor mixing conditions. In this situation the transmitted light becomes more intense and somewhat erratic. The second is related to light refraction in regions with pronounced refractive index gradients, and prevails under good mixing conditions. It can lead to positive or negative modifications of the transmitted light, the direction being dependent on the relevance of these components. The importance of the solubility of the chemical species involved, the possibility of interactions with the inner wall of the tubing, and the feasibility of dual-wavelength spectrophotometry for compensating purposes are discussed. 相似文献
953.
Six new 4,4′-substituted biphenyl coronands have been prepared. The ligands containing dimethylamino groups in the biphenyl moiety have been used in transition metal cations’ complexation and one of them (3) has demonstrated to be a selective fluorescent sensor for mercury. Stoichiometries of the formed complexes and complexation constants have been determined by titration experiments. In addition, the extractant ability of some ligands has also been studied. Finally, the electrochemical properties of some of these ligands are also described. 相似文献
954.
Fondo M Ocampo N García-Deibe AM Vicente R Corbella M Bermejo MR Sanmartín J 《Inorganic chemistry》2006,45(1):255-262
Reaction of nickel(II) acetate with H(3)L (2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) yields [Ni(2)L(OAc)(H(2)O)(2)].3MeCN.2H(2)O (1.3MeCN.2H(2)O), crystallographically characterized. 1 is unstable in solution for a long time and hydrolyzes to give [Ni(2)L(o-OC(6)H(3)BrCHO)(H(2)O)].2.25MeCN.H(2)O (2.2.25MeCN.H(2)O). In addition, 1 uptakes CO(2) from air in a basic methanol/acetonitrile solution, yielding [[Ni(2)L(MeOH)](2)(CO(3))].1.5MeOH.MeCN.H(2)O (3.1.5MeOH.MeCN.H(2)O). The X-ray characterization of 3 reveals that it is a tetranuclear nickel cluster, which can be considered as the result of a self-assembly process from two dinuclear [Ni(2)L](+) blocks, joined by a mu(4)-eta(2):eta(2)-O,O carbonate ligand. The coordination mode of the carbonate anion is highly unusual and, to the best of our knowledge, it has not been described thus far for first-row transition metal complexes or magnetically studied until now. Magnetic characterization of 1 and 3 shows net intramolecular ferromagnetic coupling between the metal atoms in both cases, with S = 2 and S = 4 ground states for 1 and 3, respectively. 相似文献
955.
A novel one-dimensional coordination polymer made up of Fe(II), 3-cyanopyridine (3CNpy), and the singular in situ formed [Cu(I)(3CNpy)(CN)2]- anionic bridge has been synthesized. This compound undergoes a spin-crossover behavior according to its magnetic and calorimetric properties. The crystal structure of the title compound has been studied in the high- and low-spin states and correlated with the character of the spin conversion. Evidence for intense spin-state-dependent Cu....Cu interactions between the chains is also reported. 相似文献
956.
Cella R Cunha RL Reis AE Pimenta DC Klitzke CF Stefani HA 《The Journal of organic chemistry》2006,71(1):244-250
[reaction: see text] Palladium(0)-catalyzed cross-coupling between potassium aryltrifluoroborate salts and aryl tellurides proceeds readily to afford the desired biaryls in good to excellent yield. The reaction seems to be unaffected by the presence of electron-withdrawing or electron-donating substituents in both the potassium aryltrifluoroborate salts and aryl tellurides partners. Biaryls containing a variety of functional groups can be prepared. A chemoselectivity study was also carried out using aryl tellurides bearing halogen atoms in the same compound. In addition, this new version of the Suzuki-Miyaura cross-coupling reaction was monitored by electrospray ionization mass spectrometry where some reaction intermediates were detected and analyzed. 相似文献
957.
Zanatta N Schneider JM Schneider PH Wouters AD Bonacorso HG Martins MA Wessjohann LA 《The Journal of organic chemistry》2006,71(18):6996-6998
A simple and regiospecific synthesis of 4-alkoxy(amino)-2-trifluoromethyl pyrroles from 5-azido-4-alkoxy(amino)-1,1,1-trifluoro-pent-3-en-2-ones by an aza-Wittig cyclization of aminophosphoranes is described. The structures of the pyrroles and their synthetic intermediates were supported by NMR and HRMS analysis. 相似文献
958.
Er, Yb Doped Yttrium Based Nanosized Phosphors: Particle Size, “Host Lattice” and Doping Ion Concentration Effects on Upconversion Efficiency 总被引:2,自引:1,他引:1
The upconverter phosphors studied herein have different percentages of Er3+ and Yb3+ as doping ions in different Y3+ matrixes (Y2O3, Y2O2S), and were prepared from different precursors (polymeric resin, oxalate, basic carbonate) and method (combustion). Upconversion emission spectra were recorded at 298 K for all the doped samples in the visible region, for efficiency and Green/Red emission relative intensity comparisons. Therefore, an investigation of the influence of the doping ion concentration, particle size and host lattice on the upconversion process is provided in view of the UPT (Upconverting phosphor technology application). On the basis of the results, it was possible to evaluate the best combination for a specific assay, considering whether it is advantageous to have the greatest contribution from the green or red emissions, or from both in comparable intensities. 相似文献
959.
The biological and toxicological effects that have been attributed to reactive nitrogen species (RNS) are increasingly stirring
the scientific inquisitiveness about the molecular mechanisms involved. However, RNS present some characteristics that complicate
their detection, namely their short lifetime and the normal presence of a variety of endogenous compounds capable of reacting
with these reactive species, when the studies are performed in biological matrices. The development of methodologies capable
of circumvent these difficulties is thus of fundamental importance. Fluorescence probes are particularly important due to
their high sensibility and usefulness in temporal and spatial monitoring of RNS, particularly in microanalysis conditions
in biological media akin to cells or tissues. In the present review is given an account of the fluorescence probes that have
been used for detection of nitric oxide (⋅NO), peroxynitrite anion (ONOO−), as well as of some of its derivatives in biological and nonbiological media. 相似文献
960.
Thaís L.A. Montanheiro Larissa S. Montagna Marcelo A. de Farias Jéssica A. Magalhães Dayane B. Tada Fabio R. Passador João Paulo B. Machado Ana Paula Lemes 《Journal of nanoparticle research》2018,20(8):206
The high hydrophilicity of cellulose nanocrystals (CNC) may result in poor dispersion in some matrices and solvents. So in this work, two different methodologies were used to reduce the hydrophilicity of CNC. In the first methodology, CNC were acetylated (CNC-Ac) in a mixture of acetic and hydrochloric acid, and in the second methodology, polyethylene glycol (PEG) was adsorbed onto CNC surface (CNC-PEG) under stirring in aqueous solution. CNC obtained by both methods were characterized by transmission electron microscopy (TEM), infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS), zeta potential, and thermogravimetric analysis (TGA). Images of TEM showed that the intrinsic morphology of cellulose was preserved after both treatments. FTIR confirmed acetylation reaction by the presence of a new band at 1732 cm?1 (acetate groups) and the consumption of OH groups. XRD showed a reduction in the crystallinity index for both applied methodologies. DLS showed reduced stability in water for CNC-Ac and CNC-PEG. Values of zeta potential changed after acetylation, from ??45 mV (CNC) to ??1 mV (CNC-Ac), and after adsorption of PEG, to ??26.7 mV (CNC-PEG). TGA showed a reduction in the thermal stability after both treatments and a change in the main degradation behavior for CNC-PEG. MTT assays showed that both proposed functionalizations induce cell proliferation, being even more evident for acetylation because, in addition to viability increase with time, it increased with the sample concentration. 相似文献