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31.
Catarina IV Ramos Flávio Figueira Marcelo D Polêto Francisco ML Amado Hugo Verli João PC Tomé M Graça PMS Neves 《Journal of mass spectrometry : JMS》2016,51(5):342-349
Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
32.
Branco TJ Botelho do Rego AM Ferreira Machado I Vieira Ferreira LF 《The journal of physical chemistry. B》2005,109(33):15958-15967
A detailed study of the luminescence decay curves of pyrene included within p-tert-butylcalix[4]arene cavities and benzophenone into silicalite channels is reported. A new methodology for a lifetime distribution analysis of the decay curve of probes onto heterogeneous surfaces is presented, which allows for asymmetric distributions and uses Voigt profiles (Gaussian and Lorentzian mixture) instead of pure Gaussian or Lorentzian distributions. Our approach uses a very simple and widely available tool for fitting, the Microsoft Excel Solver. In the case of the pyrene/tert-butylcalix[4]arene sample, the room temperature luminescence detected in the microsecond time scale was not only the phosphorescence of pyrene but also monomer delayed fluorescence, crystal phosphorescence, and excimer delayed fluorescence. In the benzophenone/silicalite case, three emissive forms of benzophenone could be assigned, one of benzophenone included into the silicalite circular zigzag channels, another for emplacement into the elliptical straight channels and finally when benzophenone is placed at the crossing points of those silicalite channels, where smaller spatial restrictions for benzophenone exist. 相似文献
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35.
Tiago A. Fernandes Adelino M. Galvão Ana M. Botelho do Rego M. Fernanda N. N. Carvalho 《Journal of polymer science. Part A, Polymer chemistry》2014,52(23):3316-3323
The number of CuCl units per camphor ligand in [{CuCl}2L]n was extended to three or four in [{CuCl}3L]n ( 2 ) or [{CuCl}4L]n ( 1 ). The Hartree‐Fock ab initio calculations support the polymeric structure of 1 and 2 that catalyze the cyclization of 4‐pentyn‐1‐oic acid ( A ) forming 5‐methylenedihydrofuran‐2(3H)‐one ( B ) and/or 2‐methyl‐5‐oxotetrahydrofuran‐2‐ylpent‐4‐ynoate ( C ). The catalytic activity of 1 , 2 and other polynuclear Cu(I) complexes ( 3–5 ) was evaluated under solvent free conditions and/or solution. In the absence of solvent, catalyst 2 displays the highest activity and selectivity (75.8/23.1, C to B ratio, at 5.4% loading) while 4 reaches the highest level of A → B conversion (97.5 %) in solution. Selected reactions were followed by NMR and the kinetic constants calculated. A mechanism is proposed based on the equations used for the calculations. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3316–3323 相似文献
36.
Thermodynamics of uptake of cadmium by Chlorella marina 总被引:1,自引:0,他引:1
Rollemberg MC Gonçalves ML Correia dos Santos MM Botelho MJ 《Bioelectrochemistry and bioenergetics (Lausanne, Switzerland)》1999,48(1):61-68
From voltammetric titration curves of living Chlorella marina cells with cadmium ion, at constant pH, the surface binding capacity of the alga was determined and interpreted in terms of average conditional equilibrium constants and of differential equilibrium function. Since the alga can live in estuaries, the influence of ionic strength and competition of alkaline and alkaline earth cations has been considered. Cadmium complexation with dead algae killed by heat or using formaldehyde has also been studied for comparison. 相似文献
37.
To determine the optimum conditions for the complete extraction of perfluorooctanoate (PFO) from polytetrafluoroethylene fluoropolymers, sample preparation and pressurized solvent extraction (PSE) conditions were investigated. Solvent extraction temperature, solvent residence time, relaxation time between extractions, and the effects of heating before PSE showed that methanol at 150 degrees C extraction temperature and a 12 min solvent residence time were the most efficient conditions. Preheating the polymer before extraction at 150 degrees C for 24 h significantly enhanced the quantity of PFO removed. Heating above 150 degrees C resulted in loss of PFO. PFO was determined by liquid chromatography with tandem mass spectrometry. 相似文献
38.
Fernanda Botelho 《Linear algebra and its applications》2010,432(1):275-282
We characterize essential normality for certain elementary operators acting on the Hilbert-Schmidt class. We find the Aluthge transform of an elementary operator of length one. We show that the Aluthge transform of an elementary 2-isometry need not be a 2-isometry. We also characterize hermitian elementary operators of length 2. 相似文献
39.
I.C. Neves G. Botelho P. Rebelo M.F.R. Pereira P. Pescarmona 《Polymer Degradation and Stability》2007,92(8):1513-1519
The catalytic degradation of high density polyethylene (HDPE) was investigated using AlTUD-1 as catalyst, a recently discovered mesoporous aluminosilicate. The catalytic activity of AlTUD-1 was evaluated by TGA measurements, using a polymer/catalyst ratio of 9:1. AlTUD-1 has a Brønsted acidic behaviour, three-dimensional (3D) connectivities and a pore diameters between 2 and 50 nm. Compared to HY zeolite, the large pore size of AlTUD-1 enhances a selective catalytic degradation of the polymer and prevents rapid deactivation. Moreover, the apparent activation energy of polymer cracking is much lower than with HY zeolite. For these reasons, AlTUD-1 is a potentially interesting catalyst for the catalytic cracking of plastic waste into liquid fuels. 相似文献
40.
Marta C. D.?Silva J. R.?Botelho Marta M.?Conceio B. F.?Lira Monyque A.?Coutinho A. F.?Dias A. G.?Souza P. F. A.?Filho 《Journal of Thermal Analysis and Calorimetry》2005,79(2):277-281
Conventional methods have been proposed to determine thermal properties of edible vegetable oils. The evaluation of the applicability of DSC and microwave oven (MO) methods to determine the specific heat capacities of the edible vegetable oils was performed. It was observed that the specific heat capacities of each edible oil increased as a function of the saturation of the fatty acids. 相似文献