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121.
Adsorption phenomena are relevant in a wide variety of subjects, from biophysics to technological applications. Different aspects, such as molecular recognition, multilayer deposition, and dynamics of polymer adsorption have been addressed. The methodologies used range from analytical and numerical methods to molecular dynamics or Monte Carlo simulations. In this work, a coarse‐grained model is used to explore the adsorption of charged backbones to oppositely charged regions of a surface. These regions encompass those small enough to prevent complete adsorption, but extend to surfaces sufficiently large to promote adsorption with minimal effect on the three‐dimensional conformation in bulk. Apart from the different surface areas explored, variations on the surface charge density, polyelectrolyte chain length, and chain stiffness were also considered. The degree of compaction of the polyelectrolyte, on adsorption, is different from that found in the bulk. Also, results indicate an nonuniform adsorption pattern on regularly charged surfaces. © 2013 Wiley Periodicals, Inc.  相似文献   
122.
The typical sidewalls produced in the fabrication of protrusion electrodes are proposed to create a low voltage (4.5 Vrms) and high transmittance (93%) blue-phase liquid crystal display (BP-LCD). The tilted electrodes produce a strong horizontal electrical field that reduces the operating voltage considerably. The common problem of the ‘dead zones’ is solved by reflecting the light onto the electrodes. In order to estimate the phase retardation of the reflected light, a ray tracing simulation program for anisotropic mediums has been developed. The proposed device is more competitive than vertical field switching based BP-LCD and also, has the advantages of protruded in-plane-switching structures. These facts make this technology a potential candidate for the next generation of BP-LCDs.  相似文献   
123.
In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D‐A) substituted 1,2,3‐triazoles as conjugative π‐linkers between the alkali metal ion receptor N‐phenylaza‐[18]crown‐6 and different fluorophoric groups with different electron‐acceptor properties (4‐naphthalimide, meso‐phenyl‐BODIPY and 9‐anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge‐transfer (CT) type probes 1 , 2 and 7 , the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge‐separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting‐up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7 , which contains a 9‐anthracenyl moiety as the electron‐accepting fluorophore, is the only probe which retains light‐up features in water and works as a highly K+/Na+‐selective probe under simulated physiological conditions. Virtually decoupled BODIPY‐based 6 and photoinduced electron transfer (PET) type probes 3 – 5 , where the 10‐substituted anthracen‐9‐yl fluorophores are connected to the 1,2,3‐triazole through a methylene spacer, show strong ion‐induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3‐triazole fluoroionophores.  相似文献   
124.
Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4‐pentanedione), triphos [1,1,1‐tris‐ (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)3], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ1O)2(H2O)(triphos)], [Ru(OAc‐κ2O,O′)(CH3SO3‐κ1O)(triphos)], [Ru(CH3SO3‐κ1O)2(H2O)(triphos)] and [Ru2(μ‐CH3SO3)3(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc‐κ1O)(OAc‐κ2O,O′)(triphos)], [Ru(CH3SO3‐κ1O)(CH3SO3‐κ2O,O′)(triphos)], H[Ru(CH3SO3‐κ1O)3(triphos)], [RuH(CH3SO3‐κ1O)(CO)(triphos)] and [RuH(CH3SO3‐κ2O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.  相似文献   
125.
A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon‐based metalloligand [κ3N‐Si(3,5‐Me2pz)3Mo(CO)3]? is presented (pz=pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5‐dimethylpyrazolyl)silanide ({Si(3,5‐Me2pz)3}?) with [Mo(CO)36‐toluene)]. The compound features a fac‐coordinated tripodal chelating ligand and an outward pointing, “free” pyramidal silyl donor, which is easily accessible for a secondary coordination to other metal centers. Several bimetallic silyl halido cuprates of the general formula [CuX{μ‐κ1Si3N‐Si(3,5‐Me2pz)3Mo(CO)3}]? (X=Cl, Br, I) have been synthesized. The electronic and structural properties of these complexes were probed in detail by X‐ray diffraction analysis, electrospray mass spectrometry, infrared‐induced multiphoton dissociation studies, cyclic voltammetry, spectroelectrochemistry, gas‐phase photoelectron spectroscopy, as well as UV/Vis and fluorescence spectroscopy. The heterobimetallic complexes contain linear two‐coordinate copper(I) entities with the shortest silicon–copper distances reported so far. Oxidation of the anionic complexes in methylene chloride and acetonitrile solutions at ${E{{0\hfill \atop 1/2\hfill}}}$ =?0.60 and ?0.44 V (vs. ferrocene/ferrocenium (Fc/Fc+)), respectively, shows substantial reversibility. Based on various results obtained from different characterization methods, as well as density functional theory calculations, these oxidation events were attributed to the Mo0/MoI redox couple.  相似文献   
126.
The small and synthetically easily accessible coumarinylmethyl backbone has been modified to generate a family of photolabile protecting groups with redshifted absorption. We relied on introducing electron‐donating groups in the 7 position and electron‐withdrawing groups in the 2‐, and 2‐ and 3 positions. In particular, we showed that the diethylamino‐thiocoumarylmethyl and the diethylamino‐coumarylidenemalononitrilemethyl are relevant for uncaging with cyan light. They both exhibit a significant action cross section for uncaging in the 470–500 nm wavelength range and a low light absorption between 350 and 400 nm. These attractive features are favorable to perform chromatic orthogonal photoactivation with UV and blue‐cyan light sources, respectively.  相似文献   
127.
In reliability theory any coherent system can be represented as either a series-parallel or a parallel-series system. Its lifetime can thus be written as the minimum of maxima or the maximum of minima. For large-scale coherent systems it is sensible to assume that the number of system components goes to infinity. Then, the possible non-degenerate extreme value laws either for maxima or for minima are eligible candidates for the system reliability or at least for the finding of adequate lower and upper bounds for the reliability. The identification of the possible limit laws for the system reliability of homogeneous series-parallel (or parallel-series) systems has already been done under different frameworks. However, it is well-known that in most situations such non-degenerate limit laws are better approximated by an adequate penultimate distribution. Dealing with regular and homogeneous parallel-series systems, we assess both theoretically and through Monte-Carlo simulations the gain in accuracy when a penultimate approximation is used instead of the ultimate one.  相似文献   
128.
129.
The present work describes the development of a sensitive and reliable analytical method based on solid‐phase extraction followed by analysis using liquid chromatography with tandem mass spectrometry for the simultaneous determination of pharmaceuticals from antibiotics (fluoroquinolones, sulfonamides, and their N4‐acetyl metabolites, and trimethoprim as sulfonamides synergist) and anthelmintics groups. SPE was optimized using different cartridges (Strata‐X, Oasis HLB, Strata C18‐E, Isolute C18, SampliQ C8/Si‐SCX). The highest recovery was achieved using Strata X cartridge (>80%) with good reproducibility (RSDs < 5%) despite various physicochemical properties of the compounds. Investigated analytes were identified and quantitatively determined by liquid chromatography with tandem mass spectrometry using multiple reaction monitoring. The method was shown to be linear over the concentration range of 0.05–30 μg/L for febantel and albendazole, and 0.10–60 μg/L for all other pharmaceuticals. Correlation coefficients were >0.99 for all compounds except for sulfamethazine (0.98). In order to demonstrate the applicability of the developed method, wastewater from the veterinary industry was analyzed. Results evidenced the presence of febantel, praziquantel, albendazole, enrofloxacin, sulfamethazine, and sulfadiazine.  相似文献   
130.
A non-denaturating isoelectric focusing (ND-IEF) gel electrophoresis protocol has been developed to study and identify uranium (U)–protein complexes with laser ablation–inductively coupled plasma mass spectrometry (LA-ICP MS) and electrospray ionization mass spectrometry (ESI-MS). The ND-IEF-LA-ICP MS methodology set-up was initiated using in vitro U–protein complex standards (i.e., U–bovine serum albumin and U–transferrin) allowing the assessment of U recovery to 64.4?±?0.4 %. This methodology enabled the quantification of U–protein complexes at 9.03?±?0.23, 15.27?±?0.36, and 177.31?±?25.51 nmol U L?1 in digestive gland cytosols of the crayfish, Procambarus clarkii, exposed respectively to 0, 0.12, and 2.5 μmol of waterborne depleted U L?1 during 10 days. ND-IEF-LA-ICP MS limit of detection was 19.3 pmol U L?1. Elemental ICP MS signals obtained both in ND-IEF electropherograms and in size exclusion chromatograms of in vivo U–protein complexes revealed interactions between U- and Fe- and Cu-proteins. Moreover, three proteins (hemocyanin, pseudohemocyanin-2, and arginine kinase) out of 42 were identified as potential uranium targets in waterborne-exposed crayfish cytosols by microbore reversed phase chromatography coupled to molecular mass spectrometry (µRPC-ESI-MS/MS) after ND-IEF separation.
Figure
The paper presents the development of a non-denaturating protocol for the separation of uranium-protein complexes by isoelectric focusing gel electrophoresis (ND-IEF) before their quantitative detection by Laser Ablation coupled to Inductively Coupled Plasma Mass Spectrometry. Potential protein targets of uranium are subsequently identified by liquid chromatography - electrospray mass spectrometry  相似文献   
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