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91.
Leonardo M. da Costa Stanislav R. Stoyanov Raimundo N. Damasceno José Walkimar de M. Carneiro 《International journal of quantum chemistry》2013,113(24):2621-2628
Density Functional Theory (UB3LYP/6‐311++G(d,p)) calculations of the affinity of the pentaaqua nickel(II) complex for a set of phosphoryl [O?P(H)(CH3)(PhR)], imino [HN?C(CH3)(PhR)], thiocarbonyl [S?C(CH3)(PhR)] and carbonyl [O?C(CH3)(PhR)] ligands were performed, where R?NH2, OCH3, OH, CH3, H, Cl, CN, and NO2 is a substituent at the para‐position of a phenyl ring.The affinity of the pentaaqua nickel(II) complex for these ligands was analized and quantified in terms of interaction enthalpy (ΔH), Gibbs free energy (ΔG298), geometric and electronic parameters of the resultant octahedral complexes. The ΔH and ΔG298 results show that the ligand coordination strength increases in the following order: carbonyl < thiocarbonyl < imino < phosphoryl. This coordination strength order is also observed in the analysis of the metal‐ligand distances and charges on the ligand atom that interacts with the Ni(II) cation. The electronic character of the substituent R is the main parameter that affects the strength of the metal‐ligand coordination. Ligands containing electron‐donating groups (NH2, OCH3, OH) have more exothermic ΔH and ΔG298 than ligands with electron‐withdrawing groups (Cl, CN, NO2). The metal‐ligand interaction decomposed by means of the energy decomposition analysis (EDA) method shows that the electronic character of the ligand modulates all the components of the metal‐ligand interaction. The absolute softness of the free ligands is correlated with the covalent contribution to the instantaneous interaction energy calculated using the EDA method. © 2013 Wiley Periodicals, Inc. 相似文献
92.
Mrcia Sousa Bispo Maria das Graas Andrade Korn Elane Santos da Boa Morte Leonardo Sena Gomes Teixeira 《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(12):2175-2180
An analytical method for separation and pre-concentration of lead in seawater for determination by inductively coupled plasma optical emission spectrometry has been investigated. Lead was retained in the solid phase (0.5 g) composed of co-precipitated naphthalene and alizarin red. The solid phase quantitatively sorbs Pb(II) at pH 8–9, and the metal was eluted using 5.0 ml of 2 mol l−1 nitric acid. The effect of NaCl, KCl, BaCl2, CaCl2, Na2SO4, MgCl2 and Na3PO4 on the sorption of Pb(II) in the solid phase was studied. A set of solutions containing varying amounts of electrolytes (0.5; 1.0; 3.0 and 5.0% m/v) with Pb (50 μg) was prepared and the recommended procedure applied. The Na3PO4 was found to interfere; the other electrolytes did not interfere up to 5% m/v. A pre-concentration factor of 40 was obtained in this analytical procedure. The limit of detection and limit of quantification for Pb(II) were 53 and 176 μg l−1, respectively. Lead was determined in seawater samples collected in Salvador city, Bahia, Brazil. The precision, expressed as R.S.D., was 1.8–4.6%, and the recovery of lead added to seawater samples was 95–97%. 相似文献
93.
Feng K De Boni L Misoguti L Mendonca CR Meador M Hsu FL Bu XR 《Chemical communications (Cambridge, England)》2004,(10):1178-1180
Two new classes of two-photon absorbing Y-shaped molecules have been developed to possess an imidazole-thiazole core and a stilbene-type conjugation pathway with either nitro or sulfonyl as terminal electron-accepting group. 相似文献
94.
Blumberger J Bernasconi L Tavernelli I Vuilleumier R Sprik M 《Journal of the American Chemical Society》2004,126(12):3928-3938
Electronic states and solvation of Cu and Ag aqua ions are investigated by comparing the Cu(2+) + e(-)--> Cu(+) and Ag(2+) + e(-)--> Ag(+) redox reactions using density functional-based computational methods. The coordination number of aqueous Cu(2+) is found to fluctuate between 5 and 6 and reduces to 2 for Cu(+), which forms a tightly bound linear dihydrate. Reduction of Ag(2+) changes the coordination number from 5 to 4. The energetics of the oxidation reactions is analyzed by comparing vertical ionization potentials, relaxation energies, and vertical electron affinities. The model is validated by a computation of the free energy of the full redox reaction Ag(2+) + Cu(+) --> Ag(+) + Cu(2+). Investigation of the one-electron states shows that the redox active frontier orbitals are confined to the energy gap between occupied and empty states of the pure solvent and localized on the metal ion hydration complex. The effect of solvent fluctuations on the electronic states is highlighted in a computation of the UV absorption spectrum of Cu(+) and Ag(+). 相似文献
95.
Silvia Tavazzi Dr. Leonardo Silvestri Dr. Luciano Miozzo Dr. Antonio Papagni Prof. Peter Spearman Dr. Sandra Ianelli Dr. Alberto Girlando Prof. Andrea Camposeo Dr. Marco Polo Dr. Dario Pisignano Dr. 《Chemphyschem》2010,11(2):429-434
Blue amplified spontaneous emission at room temperature is demonstrated from the exposed face of the strongly emitting organic semiconductor 1,1,4,4‐tetraphenyl‐1,3‐butadiene in single crystal form. The symmetry of the crystal and calculation of lattice sums indicate the J‐type organization of the molecular transition moments. The minimum in the lowest exciton dispersion branch, from which emission takes place, is found at the edge of the Brillouin zone leading to a dominant vibronic emission since the zero‐phonon line is forbidden. The observed gain narrowed line is attributed to the vibronic replica which becomes amplified with increased pumping. The reported emission is along the normal to the exposed crystal face, important for the development of vertical cavity geometry lasers based on organic single crystals. The threshold excitation fluence of 400 μJ cm?2 is comparable to other organic crystalline systems, even if the amplification path is much reduced as a consequence of the vertical geometry. Considering these relevant aspects, the optical characterization of this material is provided. The polarized absorption spectra are reported and the properties of the lowest‐energy excitonic state investigated. Calculation of the electronic transitions for the isolated molecule, lattice sums for the transition at lowest energy, and the symmetry of the crystal allow attributing the largest face of the samples and the observed optical bands in the spectra. Polarized time‐resolved spectra are also reported allowing to identify the intrinsic excitonic emission. 相似文献
96.
Eutimio G. Fernández Rodolfo Valdés Yenisley Medina José A. Montero Alejandro Figueroa Williams Ferro Yarysel Guevara Tatiana Álvarez Andrés Tamayo Regla M. Somoza Leonardo Canaán-Haden Jorge L. López 《Chromatographia》2009,70(7-8):1179-1183
Sepharose CL-4B and Sepharose CL-2B with immobilized CB.Hep-1 monoclonal antibody were compared for studying the matrix efficiency in the immunopurification of the recombinant hepatitis B surface antigen (rHBsAg). The elution capacities of both matrices were similar over eight chromatographic cycles, significant differences were only observed in the first purification cycles. A high percentage of the adsorbed rHBsAg was not eluted from both matrices. The rHBsAg purity was not affected by matrix characteristics (pore size and percentage of agarose) and differences between Sepharose CL-4B and Sepharose CL-2B do not provoke differences in the antibody released from the matrices under defined experimental conditions. 相似文献
97.
Salvatore Sotgia Ciriaco Carru Bastianina Scanu Elisabetta Pisanu Manuela Sanna Gerard Aime Pinna Leonardo Gaspa Luca Deiana Angelo Zinellu 《Analytical and bioanalytical chemistry》2009,395(8):2577-2582
A rapid and simple short-end injection capillary zone electrophoresis method was developed for the quantification of plasma
uric acid. The separation was performed in an uncoated fused-silica capillary (50 μm ID, 60 cm total length, 10.2 cm effective
length) by using as a background electrolyte a 75 mmol/L glycylglycine solution titrated with NaOH 5 mol/L to pH 9.0, a voltage
of 28 kV, a cartridge temperature of 15 °C, and direct UV detection at 292 nm. Under optimized conditions, uric acid was determinate
in little more than 1 min (1.076 minutes). In order to verify the accuracy of the analysis, urate levels were measured in
543 apparently healthy volunteers by the new assay and our previous method, and the obtained data were compared by Passing–Bablock
regression, Bland–Altman test, and a new regression-based approach, which showed a good agreement between two methods. 相似文献
98.
Andrea C. Montenegro Valentín T. Amorebieta Prof. Dr. Leonardo D. Slep Prof. Dr. Diego F. Martín Federico Roncaroli Dr. Daniel H. Murgida Prof. Dr. Sara E. Bari Dr. José A. Olabe Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(23):4213-4216
Not so elusive : [FeII(CN)5(HNO)]3? has been characterized spectroscopically after the two‐electron reduction of nitroprusside (see scheme). The complex is stable at pH 6, slowly decomposing to [Fe(CN)6]4? and N2O. It is deprotonated at increasing pH value with oxidation of bound NO? to [FeII(CN)5(NO)]3?. [FeII(CN)5(HNO)]3? is the first non‐heme iron–nitroxyl complex prepared in aqueous solution that is reversibly redox‐active under biologically relevant conditions.
99.
Maj‐Britt Suhr Kirketerp Michael Åxman Petersen Dr. Marius Wanko Dr. Leonardo Andres Espinosa Leal Henning Zettergren Dr. Françisco M. Raymo Prof. Angel Rubio Prof. Mogens Brøndsted Nielsen Prof. Steen Brøndsted Nielsen Prof. 《Chemphyschem》2009,10(8):1207-1209
From blue to red: While four π‐conjugated nitrophenolates absorb within a relatively narrow region in solution, they cover the entire visible spectrum when isolated in vacuo (see picture). The work combines gas‐ and solution‐phase spectroscopy and provides the first benchmark of theoretical excitation energies for nitrophenolates.
100.
Giovanni Pellegrino Angelo Carotti Orazio Nicolotti Leonardo Pisani Angela Stefanachi Marco Catto 《Tetrahedron letters》2010,51(13):1702-7034
A small molecular library of 40 pyrimidine, pyrazole, and isoxazole derivatives, bearing structural features for a promising binding of therapeutically interesting enzymes, was designed and prepared. An efficient and straightforward solid phase synthesis was envisaged and carried out on a Rink amide resin. The assistance of microwave heating in any step reduced the reaction time, increased the reaction yields, and allowed an easy work-up and purification of the targeted compounds. 相似文献