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61.
Despite the existence of an extensive literature, no definitive conclusion seems to emerge on the extent to which minorities are guaranteed by democratic rules in political systems. This paper contributes to this debate by proposing a modified Heigselmann and Krauss two-dimensional model of preferences in order to capture the role of abstention on minority representativeness. Regardless of the typology of abstention, simulation results show that voter abstention always benefits minorities. 相似文献
62.
Nativitat Valls Josep Bonjoch Carlos Del Alamo Joan Bosch 《Helvetica chimica acta》1992,75(1):137-144
A stereodivergent synthesis of enantiomerically pure E-nor-15-azayohimbines via condensation of tryptamine with derivatives of pyroglutamate 4 is reported. When the Pictet-Spengler reaction was induced in refluxing aqueous AcOH a nearly equimolar ratio of lactams 7 and 8 was obtained, whereas under kinetic control (TFA, room temperature) the trans-derivative 8 was the major product. In contrast, cyclization of amido acetal 12 with TsOH gave the cis-derivative 7 as preponderant component. 相似文献
63.
R. Asquini C. Chiccoli A. d’Alessandro P. Pasini C. Zannoni 《Molecular Crystals and Liquid Crystals》2019,683(1):46-55
AbstractWe present detailed Monte Carlo simulations of a simple model of a nematic liquid crystal slot waveguide shifter, investigating the effect of an applied electric external field. The simulations are based on the Lebwohl-Lasher lattice spin model with boundary conditions chosen to mimic the planar alignment as in Silicon Organic Hybrid waveguides and the homeotropic anchoring appropriate for Polydimethylsiloxane polymer walls. The external field is modeled by adding a term to the Hamiltonian which describes its coupling to the mesogenic molecules. We have investigated the effect of the external field on the optical transmission and the ordering across the cell. 相似文献
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66.
Lorenzo Chiaverini Alessandro Pratesi Damiano Cirri Arianna Nardinocchi Iogann Tolbatov Alessandro Marrone Mariagrazia Di Luca Tiziano Marzo Diego La Mendola 《Molecules (Basel, Switzerland)》2022,27(8)
Auranofin (AF, hereafter) is an orally administered chrysotherapeutic agent approved for the treatment of rheumatoid arthritis that is being repurposed for various indications including bacterial infections. Its likely mode of action involves the impairment of the TrxR system through the binding of the pharmacophoric cation [AuPEt3]+. Accordingly, a reliable strategy to expand the medicinal profile of AF is the replacement of the thiosugar moiety with different ligands. Herein, we aimed to prepare the AF analogue bearing the acetylcysteine ligand (AF-AcCys, hereafter) and characterize its anti-staphylococcal activity. Biological studies revealed that AF-AcCys retains an antibacterial effect superimposable with that of AF against Staphylococcus aureus, whereas it is about 20 times less effective against Staphylococcus epidermidis. Bioinorganic studies confirmed that upon incubation with human serum albumin, AF-AcCys, similarly to AF, induced protein metalation through the [AuPEt3]+ fragment. Additionally, AF-AcCys appeared capable of binding the dodecapeptide Ac-SGGDILQSGCUG-NH2, corresponding to the tryptic C-terminal fragment (488–499) of hTrxR. To shed light on the pharmacological differences between AF and AF-AcCys, we carried out a comparative experimental stability study and a theoretical estimation of bond dissociation energies, unveiling the higher strength of the Au–S bond in AF-AcCys. From the results, it emerged that the lower lipophilicity of AF-AcCys with respect to AF could be a key feature for its different antibacterial activity. The differences and similarities between AF and AF-AcCys are discussed, alongside the opportunities and consequences that chemical structure modifications imply. 相似文献
67.
Coutinho CF Coutinho LF Mazo LH Nixdorf SL Camara CA Lanças FM 《Analytica chimica acta》2007,592(1):30-35
A simple, rapid, and low-cost coulometric method for direct detection of glyphosate using hydrophilic interaction chromatography is presented. The principle of detection is based on the enhancement of the anodic current of copper microelectrode in the presence of complexing agents, such as glyphosate, with the formation of a soluble Cu(II) complex. Under optimized conditions, the limit of detection (S/R = 3) for glyphosate was 0.1 mg L−1 (0.59 μM) without any preconcentration method. The calibration curve has been found linear in all concentration range tested (from limit of detection to 34 mg L−1) with an excellent correlation coefficient (0.9999). The present method was successfully applied for the determination of glyphosate in fruit juices without any kind of extraction, clean-up, or preconcentration step, with recoveries of 92 and 90% for apple and grape juice, respectively. 相似文献
68.
Saracino MA Mercolini L Musenga A Bugamelli F Raggi MA 《Journal of separation science》2008,31(10):1851-1859
Three analytical methods have been developed and compared for the quality control of a new formulation (Soymen GN(R) capsules) containing soy extract and melatonin for the treatment of menopausal symptoms. The first method is based on MEKC with diode-array detection, using a mixture of basic carbonate buffer (95%) and methanol (5%), containing 55 mM SDS, as the BGE. The second method is an HPLC method with UV detection at 260 nm. The third method is an HPLC method coupled to amperometric detection which is carried out at an oxidation potential of +0.8 V. In both HPLC systems, the chromatographic separation is obtained on an RP C18 column using a mixture of ACN and an acidic phosphate buffer (25:75 v/v) as the mobile phase. A feasible pretreatment procedure with a methanol/water mixture has been implemented to achieve the quantitative extraction of the main soy isoflavones and of melatonin from the capsules. The results obtained with the three methods are in good agreement with each other and satisfactory in terms of linearity (r(2) >0.9996), precision (RSD <5.4%) and accuracy (recovery >97%). Thus, each of the three analytical methods seems to be suitable for the simultaneous analysis of the main soy isoflavones and melatonin in the new commercial formulation. 相似文献
69.
Carlos M. Silva Poliana L. Silva Josefredo R. Pliego 《International journal of quantum chemistry》2014,114(8):501-507
Experimental kinetics of sulfide oxidation by hydrogen peroxide presents a pH‐dependent profile. In this article, it was carried out a detailed study of the mechanism and kinetics of dimethyl sulfide (DMS) oxidation by H2O2 in neutral, acid, and basic aqueous medium using ab initio calculations. The results point out that DMS oxidation in neutral aqueous medium occurs through its direct reaction with H2O2. In acid medium, cluster‐continuum model calculations shows that cluster is the best representation of the very reactive species. In basic medium, there is formation of the species. However, the pathway involving this species has high free energy barrier, making this pathway unfeasible. The theoretical pH‐rate profile is in good agreement with the experimental observations. © 2013 Wiley Periodicals, Inc. 相似文献
70.
We study the diabatic crossing of two electronic surfaces from the time-dependent point of view, looking at the time and frequency-resolved spontaneous emission spectra and to the total population of the excited state, which for a pump and-probe experiment with two δ-like pulses, is proportional to the total emission. The results of some computations on a model case are presented and discussed. 相似文献