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51.
52.
The synthesis and electrochemical, optical, and ion-sensing properties of ferrocene-imidazophenazine dyads are presented. Dyad 4 behaves as a highly selective chemosensor molecule for Pb(2+) cations in CH(3)-CN/H(2)O (9:1). The emission spectrum (λ(exc) = 317 nm) undergoes an important chelation-enhanced fluorescence effect (CHEF = 47) in the presence of Pb(2+) cations, a new low-energy band appeared at 502 nm, in its UV/vis spectrun, and the oxidation redox peak is anodically shifted (ΔE(1/2) = 230 mV). The presence of Hg(2+) cations also induced a perturbation of the redox potencial although in less extension than those found with Pb(2+) cations. Dyad 7, bearing two fused pyridine rings, has shown its ability for sensing Hg(2+) cations selectively through three channels: electrochemical, optical, and fluorescent; the oxidation redox peak is anodically shifted (ΔE(1/2) = 200 mV), a new low-energy band of the absorption spectrum appeared at 485 nm, and the emission spectrum (λ(exc) = 340 nm) is red-shifted by 32 nm accompanied by a remarkable chelation-enhanced fluorescent effect (CHEF = 165). Linear sweep voltammetry revealed that Cu(2+) cations induced oxidation of the ferrocene unit in both dyads. (1)H NMR studies have been carried out to obtain information about the molecular sites which are involved in the binding process. 相似文献
53.
Guillermina L. Estiú Alicia H. Jubert Jos Molina Juan Costamagna Juan Canales Juan Vargas 《Journal of Molecular Structure》1995,330(1-3):201-210
Semiempirical self-consistent field (SCF) and configuration interaction (CI) calculations of the intermediate neglect of differential overlap (INDO) type are applied to the analysis of the electronic transitions of the hexaazacyclophane base and its Ni and Cu complexes. The ground states (1Ag for the ligand and Ni complex, 2B1g for the Cu complex) are planar structures of D2h symmetry. The low-energy region of the UV-visible spectra, whose analysis may help to recognize the catalytic active sites of the complexes is associated with d → d transitions in the Ni complex, and M → L charge transfer in the Cu complex. 相似文献
54.
Bart G. Manders Alex M. van Herk Anton L. German 《Macromolecular theory and simulations》1995,4(2):325-333
The Monte Carlo method has been used for numerically simulating pulsed-laser polymerization (PLP) in microemulsion, in order to establish if a shift from inflection point to peak maximum as the best measure of the propagation rate constant, kp, will occur theoretically. Termination is assumed to be instantaneous in the simulations as droplet sizes can be very small in microemulsions. From the results of the simulations it is found that instantaneous termination indeed causes the peak maximum to become the best measure of kp. From these results it can be deduced that in bulk it is not simply the Poisson-broadening that causes the peak maximum to yield an overestimation of kp. This overestimation is rather caused by the fact that the termination rate is finite leading to an asymmetrical peak in the molecular weight distribution. In combination with broadening this yields the inflection point to be the best measure of kp in the bulk. 相似文献
55.
Cardiovascular disease and cancer are the main causes of morbidity and mortality worldwide. Thus, investigators have focused their efforts on gaining insight into understanding the mechanisms involved in the development and evolution of these diseases. In the past decade, and with the contribution of the -omics technologies, strong evidence has supported an essential role of gene-nutrient interactions in these processes, pointing at natural bioactive molecules as promising complementary agents that are useful in preventing or mitigating these diseases. In addition, alterations in lipid metabolism have recently gained strong interest since they have been described as a common event required for the progression of both diseases. In the present review, we give an overview of lipid metabolism, mainly focusing on lipoprotein metabolism and the mechanisms controlling lipid homeostasis. In addition, we review the modulation of lipid metabolism by bioactive molecules, highlighting their potential use as therapeutic agents in preventing, and treating chronic diseases such as cardiovascular disease and cancer. Finally, we report the usefulness of the -omics technologies in nutritional research, focusing on recent findings, within nutritional genomics, in the interaction of bioactive components from foods with several genes that are involved in the development and progression of these diseases. 相似文献
56.
K. E. German S. V. Krjuchkov L. I. Belyaeva V. I. Spitsyn 《Journal of Radioanalytical and Nuclear Chemistry》1988,121(2):515-521
The solubility of tetraalkylammonium pertechnetates in aqueous electrolyte solutions has been studied. It does not practically depend on ionic strength of the solution when specific interaction of own ions and ions of the dissolved electrolyte (e.g. LiNO3 up to 5 mol/l) does not occur. A remarkable dependence of Bu4NTcO4 solubility on acidity of the solution has been found. The influence of ion association on the solubility is discussed. 相似文献
57.
Otón F Tárraga A Velasco MD Molina P 《Dalton transactions (Cambridge, England : 2003)》2005,(7):1159-1161
A ferrocene-based heteroditopic receptor containing urea and crown ether units shows electrochemical responses to dihydrogenphosphate and fluoride anions. K+ cations can only be detected in the presence of dihydrogenphosphate. 相似文献
58.
Caitlin E. Karver Eric S. Molina Erin T. Economos Jonathan C. Fuentes Socrates M. Kaitson Samuel Kogan 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(2):101-105
Electrophilic trisubstituted ethylenes, halogen ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2CH3 (where R is 3-Br-4-CH3O, 5-Br-2-CH3O, 2-F-5-CH3, 2-F-6-CH3, 4-F-3-CH3, 4-F-3-PhO, 2-F-5-I, 2-F-6-I, 2-F3C, 4-F3C) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and methyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. The order of relative reactivity (1/r 1) for the monomers is 2-F-5-CH3 (6.4) > 4-F-3-PhO (5.6) > 4-F3C (4.8) > 3-Br-4-CH3O (3.7) > 2-F-5-I (3.6) > 2-F3C (2.2) > 2-F-6-I (2.1) > 5-Br-2-CH3O (1.9) > 4-F-3-CH3 (1.8) > 2-F-6-CH3 (1.2). Relatively high T g of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (2–21% wt), which then decomposed in the 500–800°C range. 相似文献
59.
Barbara Bojko Krzysztof Gorynski German Augusto Gomez-Rios Jan Matthias Knaak Tiago Machuca Vinzent Nikolaus Spetzler Erasmus Cudjoe Michael Hsin Marcelo Cypel Markus Selzner Mingyao Liu Shaf Keshavjee Janusz Pawliszyn 《Analytica chimica acta》2013
Metabolomics and biomarkers discovery are an integral part of bioanalysis. However, untargeted tissue analysis remains as the bottleneck of such studies due to the invasiveness of sample collection, as well as the laborious and time-consuming sample preparation protocols. In the current study, technology integrating in vivo sampling, sample preparation and global extraction of metabolites – solid phase microextraction was presented and evaluated during liver and lung transplantation in pig model. Sampling approaches, including selection of the probe, transportation, storage conditions and analyte coverage were discussed. The applicability of the method for metabolomics studies was demonstrated during lung transplantation experiments. 相似文献
60.
Abstract Neurotoxicities of a series of solvents in rats and mice have been modeled by means of the TOPS-MODE approach. Two quantitative structure-toxicity relationship (QSTR) models were obtained explaining more than 80% of the variance in the experimental values of neurotoxicity of 45 solvents. Only one compound was detected as statistical outlier for these models. In contrast, previous models explained less than 60% of the variance in this property for 44 solvents. Finally, the contributions to neurotoxicity in rats and mice for a series of structural fragments were found. Structural characteristics of chlorinated fragments responsible for their different neurotoxicities were analyzed. The differences in neurotoxic behavior of some fragments in rats and mice were also analyzed, which could give insights on the toxicological mechanism of action of solvents studied. 相似文献