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181.
Second-order calibration methods are gaining widespread acceptance among the analytical community mainly because: (1) a wide range of analytical instrumentation is available that enables high dimensionality data to be obtained; (2) the chemometric techniques for treating these data are highly developed; and (3) they have the so-called “second-order advantage”, i.e. they can predict the concentration of the analyte of interest even in the presence of unknown interferents. This also enables several analytes to be determined simultaneously.In this paper we describe the most common instrumental and chemometric techniques used in second-order calibration and discuss their applications since 2000. First, we introduce briefly the techniques and then we comment the applications. Given the practical nature of this paper, we have classified the techniques according to five fields of application: pharmaceuticals, biological matrices, foods, environmental matrices and synthetic matrices. 相似文献
182.
Binary oxides of elements belonging to groups 13-15 are of special relevance from a fundamental point of view as well as because of their technological applications as a basis in zeotypes, glasses, or semiconductors. Aluminum oxide, Al2O3, crystallizes in the corundum structure, which is stable at low and high pressures, with the Al showing octahedral coordination. Silicon oxide, SiO2, crystallizes in phases with tetrahedral Si coordination at low pressures as alpha-quartz, but at high pressures, octahedral coordination is stable in the stishovite polymorph. The only known binary phosphorus(V) oxides have tetrahedral P coordination. We have studied the stability of different phases of P2O5 at high pressure, applying density functional theory methodology within the local density and generalized gradient approximations and a plane-wave basis set. Our results indicate that the most stable form of P2O5 at high pressure could be one with hexacoordinated phosphorus. All of the high-pressure phases of Al, Si, and P can be described as a different linking of the same rutile-type blocks. 相似文献
183.
The all-trans pentaene, 3,12-di(tert-butyl)-2,2,13,13-tetramethyl-3,5,7,9,11-tetradecapentaene (ttbP5) fluoresces in two different regions of the visible spectrum. It produces an extremely weak emission in the gas phase that can also be detected in the condensed phase; such an emission exhibits a negligible Stokes shift with respect to the 1Ag-->1Bu absorption transition and can in principle be assigned to the 1Bu-->1Ag emission of the compound. ttbP5 also exhibits a second fluorescence emission at approximately 520 nm in both the gas phase and the condensed phase. The emission in the condensed phase increases in strength and structure, with no change in spectral position, as the solvent viscosity increases by effect of the solution temperature being lowered. The spectral behavior of this pentaene (ttbP5) is different enough from that reported [J. Catalan et al., J. Chem. Phys. 128, 104504 (2008)] for its tetraene counterpart (ttbP4) to warrant a separate analysis in order to facilitate a better understanding of the way the photophysics of these polyenes changes as their chain is lengthened. 相似文献
184.
Regina Pamplona Sandra González-Lana Pilar Romero Ignacio Ochoa Rafael Martín-Rapún Carlos Sánchez-Somolinos 《Macromolecular bioscience》2023,23(12):2300227
From the first experiments with biomaterials to mimic tissue properties, the mechanical and biochemical characterization has evolved extensively. Several properties can be described, however, what should be essential is to conduct a proper and physiologically relevant characterization. Herein, the influence of the reaction media (RM) and swelling media (SM)–phosphate buffered saline (PBS) and Dulbecco's modified Eagle's medium (DMEM) with two different glucose concentrations–is described in gelatin methacrylamide (GelMA) hydrogel mechanics and in the biological behavior of two tumoral cell lines (Caco-2 and HCT-116). All scaffolds are UV-photocrosslinked under identical conditions and evaluated for mass swelling ratio and stiffness. The results indicate that stiffness is highly susceptible to the RM, but not to the SM. Additionally, PBS-prepared hydrogels exhibited a higher photopolymerization degree according to high resolution magic-angle spinning (HR-MAS) NMR. These findings correlate with the biological response of Caco-2 and HCT-116 cells seeded on the substrates, which demonstrated flatter morphologies on stiffer hydrogels. Overall, cell viability and proliferation are excellent for both cell lines, and Caco-2 cells displayed a characteristic apical-basal polarization based on F-actin/Nuclei fluorescence images. These characterization experiments highlight the importance of conducting mechanical testing of biomaterials in the same medium as cell culture. 相似文献
185.
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187.
Ramos PH Coumans RG Deutman AB Smits JM de Gelder R Elemans JA Nolte RJ Rowan AE 《Journal of the American Chemical Society》2007,129(17):5699-5702
The threading behavior of a zinc analogue of a previously reported processive manganese porphyrin catalyst onto a series of polymers of different lengths is reported. It is demonstrated that the speed of the threading process is determined by the opening of the cavity of the toroidal porphyrin host, which can be tuned with the help of axial ligands that coordinate to the metal center in the porphyrin. 相似文献
188.
A new and original analytical method was developed for the routine analysis of 28 multiclass pesticide residues in vegetables (green pepper, red pepper, and tomato). The extraction was performed with acetone, and the pesticides were partitioned into ethyl acetate-cyclohexane (1 + 1, v/v). Residue levels in vegetables were determined by gas chromatography (GC) with electron-capture detection. Residue identities were confirmed by GC coupled with mass spectrometry in the selected ion monitoring mode. The average recoveries in pepper and tomato obtained for all analytes studied were 67.3 and 123.1%, respectively, with relative standard deviation between 1.8 and 7.0%. The detection limit for the pesticides studied varied from 0.1 to 2.6 microg/kg. The proposed method was applied to the analysis of these compounds in vegetables grown in experimental greenhouses. 相似文献
189.
Rayón VM Redondo P Barrientos C Largo A 《The journal of physical chemistry. A》2007,111(28):6345-6353
A theoretical study of the first-row transition metal dicarbide cations MC2+ (M=Sc-Zn) has been carried out. Predictions for different molecular properties that could help in their eventual experimental detection have been made. Most MC2+ compounds prefer a C2v symmetric arrangement over the linear geometry. In particular, the C2v isomer is specially favored for early transition metals. Only for CuC2+ is the linear isomer predicted to be the global minimum, although by only 1 kcal/mol. In all cases the isomerization barrier between cyclic and linear species seems to be very small (below 2 kcal/mol). The topological analysis of the electronic density shows that most C2v isomers are T-shaped structures. In general, MC2+ compounds for early transition metals have larger dissociation energies than those formed by late transition metals. In most cases the dissociation energies for MC2+ compounds are much smaller than those obtained for their neutral analogues. An analysis of the bonding in MC2+ compounds in terms of the interactions between the valence orbitals of the fragments helps to interpret their main features. 相似文献
190.
Castellote I Morón M Burgos C Alvarez-Builla J Martin A Gómez-Sal P Vaquero JJ 《Chemical communications (Cambridge, England)》2007,(12):1281-1283
Imines react with N-iodosuccinimide (NIS) to afford unexpected 1 : 1 complexes and the structure of one of these was determined by single-crystal X-ray diffraction; the reaction seems to be very general for substituted cyclic imines with solid stable complexes obtained in high yields; this is the first reported example of a halogen bonding interaction involving the C=N bond and NIS. 相似文献