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11.
A study of the mechanisms involved in the separation of metal ions with a mixed-bed stationary phase
Summary The optimization of chromatographic methods for the determination of metal species require an understanding of the mechanisms
involved. In this work, the separation of Cd, Co, Cu, Fe(II/III), Mn, Pb and Zn using a mixed bed column (IonPac CS5A) and
a cation-exchange column (IonPac CS2) is studied as a function of mobile phase composition. The type and concentration of
complexing agent and of ionic strength modificators were evaluated. The charge of analytes were calculated using the classical
ion exchange approach to highlight the effect of eluent composition on retention. The comparative study enabled us to identify
an optimal eluent composition for the separation of the nine metal species. 相似文献
12.
De Fazio D Lucas JM Aquilanti V Cavalli S 《Physical chemistry chemical physics : PCCP》2011,13(18):8571-8582
Exact quantum reactive scattering calculations in the collision energy range 1-250 meV have been carried out for both the isotopic product channels of the title system. The dynamical studies compares an ab initio potential energy surface (PES) recently appeared in the literature (J. Chem. Phys., 2008, 129, 011103) with other phenomenological PESs. Vibrational branching ratios, cross sections and rate constants are presented and compared with molecular beam scattering experiments as well as with chemical kinetics data. In particular, the agreement of the vibrational branching ratios with experimental measurements is improved with respect to previous studies on other PESs, mainly because of the presence of a broad peak in the HF(v' = 3) integral cross section completely absent in the previous simulations. This feature, observed by molecular beam experiments, is the fingerprint of a new reaction mechanism operative in the dynamics described by the new PES. A conjecture for its origin, able to explain many of its characteristic aspects, is analyzed and discussed. 相似文献
13.
Migani A Gentili PL Negri F Olivucci M Romani A Favaro G Becker RS 《The journal of physical chemistry. A》2005,109(39):8684-8692
The efficiency of the photochemical ring-opening of chromenes (or benzopyrans) depends on the vibronic transition selected by the chosen excitation wavelength. In the present work, ab initio CASPT2//CASSCF calculations are used to determine the excited-state ring-opening reaction coordinate for 2H-chromene (C) and 2,2-diethyl-2H-chromene (DEC) and provide an explanation for such an unusual mode-dependent behavior. It is shown that excited-state relaxation and decay occur via a multimodal and barrierless (or nearly barrierless) reaction coordinate. In particular, the relaxation out of the Franck-Condon involves a combination of in-plane skeletal stretching and out-of-plane modes, while the second part of the reaction coordinate is dominated exclusively by a different out-of-plane mode. Population of this last mode is shown to be preparatory with respect to both C-O bond breaking and decay via an S(1)/S(0) conical intersection. The observed mode-dependent ring-opening efficiency is explained by showing that the vibrational mode corresponding to the most efficient vibronic transition has the largest projection onto the out-of-plane mode of the reaction coordinate. To support the computationally derived mechanism, we provide experimental evidence that the photochemical ring-opening reaction of 2,2-dimethyl-7,8-benzo(2H)chromene, that similarly to DEC exhibits a mode-dependent photoreaction, has a low ( approximately 1 kcal mol(-1)) activation energy barrier. 相似文献
14.
Summary The influence of the distance between the solvent entry and the starting zone positions, Z0, on the average plate height was studied. This factor was found to be of major importance and could be optimized. The Guiochon and Siouffi model greatly underestimates the plate height for low values of Z0. 相似文献
15.
Braga D Maini L de Sanctis G Rubini K Grepioni F Chierotti MR Gobetto R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(22):5538-5548
Mechanical mixing of solid dicarboxylic acids of variable chain length HOOC(CH(2))(n)COOH (n = 1-7) with solid 1,4-diazabicyclo[2.2.2]octane generates the corresponding salts or co-crystals of the formula [N(CH(2)CH(2))(3)N]-H-[OOC(CH(2))(n)COOH] (n=1-7). Preparation of the same systems from solution has been instrumental for a full characterization of the mechanochemical products by means of single-crystal and powder-diffraction X-ray analyses, as well as by solid-state NMR. The acid-base adducts, whether involving proton transfer from the COOH group to the N-acceptor, that is having ((-))O...H-N((+)) interactions, or the formation of neutral O-H...N hydrogen bonds, show a melting point alternation phenomenon analogous to that shown by the neutral carboxylic acids. The carbon chemical shift tensors of the COOH group obtained from the sideband intensity of low speed spinning NMR spectra provide a reliable criterion for assigning the protonation state of the adducts. 相似文献
16.
Francesco Demartin Fabrizia Fabrizi de Biani Cristina Femoni Maria Carmela Iapalucci Giuliano Longoni Piero Macchi Piero Zanello 《Journal of Cluster Science》2001,12(1):61-74
The [Ni36Pt4(CO)45]6- and [Ni37Pt4(CO)46]6- clusters have been obtained in mixture upon reaction in acetonitrile of [Ni6(CO)12]2- salts with K2PtCl4 in a 2.5:1 molar ratio. The two hexaanions were indistinguishable by spectroscopic techniques. Crystallization of their trimethylbenzylammonium salts led to crystals of composition 0.5[NMe3CH2Ph]6[Ni36Pt4(CO)45]-0.5[NMe3CH2Ph]6[Ni37Pt4(CO)46]·C3H8O, hexagonal,space group P63 (No. 173), a=17.853(9), c=27.127(13) Å, Z=2; final R=0.057. The metal core of the [Ni36Pt4(CO)45]6- anion consists of a Pt4 tetrahedron fully encapsulated in a shell of 36 Ni atoms belonging to a very distorted and incomplete 5 tetrahedron. The [Ni37Pt4(CO)46]6- hexaanion derives from the former by capping the unique triangular face of the metal polyhedron with an additional Ni(CO) fragment. The [Ni36Pt4(CO)45]6--[Ni37Pt4(CO)46]6- mixture is rapidly degraded to the known [Ni9Pt3(CO)21]4- cluster by exposure to carbon monoxide. Its reaction with protic acids initially affords the corresponding [H6-nNi36Pt4(CO)45]n--[H6-nNi37Pt4(CO)46]n- (n=5, 4) derivatives, and eventually leads to rearrangement to the known [H6-n Ni38Pt6(CO)48]n- species. Both [Ni36Pt4(CO)45]6--[Ni37Pt4(CO)46]6- and [HNi36Pt4(CO)45]5--[HNi37Pt4(CO)46]5- mixtures have been chemically and electrochemically reduced to their corresponding [Ni36Pt4(CO)45]n--[Ni37Pt4(CO)46]n- (n=7–9) and [HNi36Pt4(CO)45]n--[HNi37Pt4(CO)46]n- (n=6–8) mixtures. 相似文献
17.
Dario Braga Fabrizia Grepioni Paul J. Dyson Brian F. G. Johnson 《Journal of Cluster Science》1992,3(3):297-311
The molecular and crystal structures of a number of ruthenium and osmium clusters of nuclearity between three and six containing arene fragments such as C6H6, C6H3Me3, C6H4Me2 and C6H5Me have been investigated. Attention has been focused on the relationship between the terminal (
6-coordination) and face-capping (
3:
2:
2:
2-coordination) bonding modes. Empirical packing potential energy calculations have been employed to investigate the intermolecular organization in the crystal. It has been shown that the arene fragments in mono-arene clusters form ribbons, while in bis-arene clusters graphitic-like interactions throughout the crystal are established. The factors controlling the ease of arene reorientational motion in the solid state has also been investigated in relation to the shape, size and geometry of the molecules and of their interlocking modes. 相似文献
18.
Dynarowicz-L&acedil;tka P Kita K Milart P Dhanabalan A Cavalli A Oliveira ON 《Journal of colloid and interface science》2001,239(1):145-157
A series of 5'-phenyl-m-terphenyl carboxylic acid (PTCA) derivatives with methyl, chloro, and fluoro substituents at both side phenyl rings have been synthesized and characterized as Langmuir monolayers at the air/water interface. A comparative analysis, based on the surface pressure and electric surface potential measurements under a variety of experimental conditions, is complemented with BAM images. Copyright 2001 Academic Press. 相似文献
19.
Ab initio CASPT2//CASSCF relaxation path computations are employed to determine the intrinsic (e.g., in vacuo) mechanism underlying the rise and decay of the luminescence of the anionic form of the green fluorescent protein (GFP) fluorophore. Production and decay of the fluorescent state occur via a two-mode reaction coordinate. Relaxation along the first (totally symmetric) mode leads to production of the fluorescent state that corresponds to a planar species. The second (out-of-plane) mode controls the fluorescent state decay and mainly corresponds to a barrierless twisting of the fluorophore phenyl moiety. While a "space-saving" hula-twist conical intersection decay channel is found to lie only 5 kcal mol(-1) above the fluorescent state, the direct involvement of a hula-twist deformation in the decay is not supported by our data. The above results indicate that the ultrafast fluorescence decay observed for the GFP chromophore in solution is likely to have an intrinsic origin. The possible effects of the GFP protein cavity on the fluorescence lifetime of the investigated chromophore model are discussed. 相似文献
20.
Maria Helena Araujo Maria D. Vargas Anthony G. Avent Fabrizia Grepioni 《Journal of organometallic chemistry》2004,689(22):3513-3519
The reactions of [HIr4(CO)9(Ph2PCCPh)(μ-PPh2)] (1) or [Ir4(CO)8(μ3-η2-HCCPh)(μ-PPh2)2] (2) with HCCPh gave two isomeric forms of [Ir4(CO)6(μ3-η2-HCCPh)(μ2-η4-C4H2Ph2)(μ-PPh2)2] (3 and 4) in good yields as the only products. These compounds were characterized with analytical and spectroscopic data including 1H, 13C and 31P NMR (1 and 2D) spectroscopy and their molecular structures were established by X-ray diffraction studies. Compounds 3 and 4 exhibit the same distorted butterfly metal polyhedral arrangement of metal atoms with two μ-PPh2 that occupy different positions in the structures of the two isomers. Both molecules contain a HCCPh ligand bonded in a μ3-η2-// mode to one of the wings of the butterfly and a metallacyclic ring, which resulted from head-to-tail coupling, in the case of [Ir4(CO)6(μ3-η2-HCCPh){μ2-η4-(H)CC(Ph)C(H)C(Ph)}(μ-PPh2)2] (3) and tail-to-tail coupling, in that of [Ir4(CO)6(μ3-η2-HCCPh){μ2-η4-(H)CC(Ph)C(Ph)C(H)}(μ-PPh2)2] (4), and which is linked to two metal atoms of the second wing of the butterfly. 相似文献