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991.
992.
A semi‐quantitative approach for the rapid screening and mass profiling of naphthenic acids directly in contaminated aqueous samples 下载免费PDF全文
Kyle D. Duncan Dane R. Letourneau Gregory W. Vandergrift Karl Jobst Eric Reiner Chris G. Gill Erik T. Krogh 《Journal of mass spectrometry : JMS》2016,51(1):44-52
We report the use of a direct sampling, online analytical approach for the determination of acid extractable naphthenic acids in complex aqueous samples, known as condensed phase membrane introduction mass spectrometry (CP‐MIMS). The technique employs a capillary hollow fibre semi‐permeable membrane probe configured for immersion into a pH adjusted sample. A continuously flowing methanol acceptor phase transfers naphthenic acids to an electrospray ionization source, operated in negative ion mode, whereupon they are analysed by mass spectrometry as [M–H]? ions. High‐resolution mass spectrometry is used to characterize the influence of sample pH on membrane transport of multiple components of complex naphthenic acid mixtures. We demonstrate the use of CP‐MIMS for semi‐quantitative analysis of real‐world samples using selected ion monitoring and full scan mass spectra at unit mass resolution. The technique has also been employed to continuously monitor the temporal evolution in the mass profile and concentrations of individual naphthenic acid isomer classes in heterogeneous solutions during adsorption processes. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
993.
Haghedooren E Farkas E Kerner A Dragovic S Noszál B Hoogmartens J Adams E 《Talanta》2008,76(1):172-182
In order to study column deterioration as a result of long-term storage and/or usage in liquid chromatography analyses, 55 pairs (same batch) of different commercial reversed-phase C(18) columns were examined using an already existing column characterisation system. After initial testing, one column was stored and the other was used to analyse different pharmaceuticals. All columns were characterized by four chromatographic parameters reflecting hydrophobicity, silanol activity, metal impurity and steric selectivity at the beginning and at the end of the test. An F-value was calculated to express the change of column properties with one single number. After performing analyses, higher F-values were obtained as compared to the non-used, stored columns. Although the time during which the columns were used to perform analyses was relatively short, an obvious influence was noticed, mainly resulting from small changes in silanol activity and hydrophobicity. Most of the affected columns have no endcapping and/or no base deactivation, making them more vulnerable for degradation, resulting in higher silanol activity and faster ageing. This effect is observed less with columns equipped with polar-embedded groups and/or polar endcapping, protecting the column by blocking the silanol groups and attracting a shielding water layer. Also columns with higher coverages and bulky or long chains show more resistance towards degradation. 相似文献
994.
Storr T Verma P Pratt RC Wasinger EC Shimazaki Y Stack TD 《Journal of the American Chemical Society》2008,130(46):15448-15459
The geometric and electronic structure of an oxidized Cu complex ([CuSal](+); Sal = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV-vis-NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal](+) (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal](+), affording exclusively a Cu(III) species in the solid state (4-300 K). Variable-temperature solution studies suggest that [CuSal](+) exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal(*)](+) (S = 1) and the high-valent metal form [Cu(III)Sal](+) (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine-bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSal(red)](+) (Sal(red) = N,N'-bis(3,5-di- tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)-ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu-bis-phenoxide complexes. 相似文献
995.
Palermo V Otten MB Liscio A Schwartz E de Witte PA Castriciano MA Wienk MM Nolde F De Luca G Cornelissen JJ Janssen RA Müllen K Rowan AE Nolte RJ Samorì P 《Journal of the American Chemical Society》2008,130(44):14605-14614
The physicochemical properties of organic (multi)component films for optoelectronic applications depend on both the mesoscopic and nanoscale architectures within the semiconducting material. Two main classes of semiconducting materials are commonly used: polymers and (liquid) crystals of small aromatic molecules. Whereas polymers (e.g., polyphenylenevinylenes and polythiophenes) are easy to process in solution in thin and uniform layers, small molecules can form highly defined (liquid) crystals featuring high charge mobilities. Herein, we combine the two material types by employing structurally well-defined polyisocyanopeptide polymers as scaffolds to precisely arrange thousands of electron-accepting molecules, namely, perylenebis(dicarboximides) (PDIs), in defined chromophoric wires with lengths of hundreds of nanometers. The polymer backbone enforces high control over the spatial location of PDI dyes, favoring both enhanced exciton and charge transfer. When blended with an electron-donor system such as regioregular poly(3-hexylthiophene), this polymeric PDI shows a relative improvement in charge generation and diffusion with respect to monomeric, aggregated PDI. In order to correlate this enhanced behavior with respect to the architecture, atomic force microscopy investigations on the mixtures were carried out. These studies revealed that the two polymers form interpenetrated bundles having a nanophase-segregated character and featuring a high density of contact points between the two different phases. In order to visualize the relationship between the architecture and the photovoltaic efficiency, Kelvin probe force microscopy measurements were carried out on submonolayer-thick films. This technique allowed for the first time the direct visualization of the photovoltaic activity occurring in such a nanoscale phase-segregated ultrathin film with true nanoscale spatial resolution, thus making possible a study of the correlation between function and architecture with nanoscale resolution. 相似文献
996.
Palyvoda O Bordenyuk AN Yatawara AK McCullen E Chen CC Benderskii AV Auner GW 《Langmuir : the ACS journal of surfaces and colloids》2008,24(8):4097-4106
The attachment of cells onto solid supports is fundamental in the development of advanced biosensors or biochips. In this work, we characterize cortical neuron adhesion, growth, and distribution of an adhesive layer, depending on the molecular structure and composition . Neuronal networks are successfully grown on amino-terminated alkanethiol self-assembled monolayer (SAM) on a gold substrate without adhesion protein interfaces. Neuron adhesion efficiency was studied for amino-terminated, carboxy-terminated, and 1:1 mixed alkanethiol SAMs deposited on gold substrates. Atomic force microscopy and X-ray photoelectron spectroscopy were used to measure the roughness of gold substrate and thickness of SAM monolayers. Conformational ordering and ionic content of SAMs were characterized by vibrational sum frequency generation (VSFG) spectroscopy. Only pure amino-terminated SAMs provide efficient neuronal cell attachment. Ordering of the terminal amino groups does not affect efficiency of neuron adhesion. VSFG analysis shows that ordering of the terminal groups improves with decreasing surface roughness; however the number of gauche defects in alkane chains is independent of surface roughness. We monitor partial dissociation of carboxy groups in mixed SAMs that implies formation of NH3+ neighbors and appearance of catanionic structure. Such catanionic environment proved inefficient for neuron adhesion. Surface roughness of metal within the 0.7-2 nm range has little effect on the efficiency of neuron adhesion. This approach can be used to create new methods that help map structure-property relationships of biohybrid systems. 相似文献
997.
Zuidema E Sarmentero MA Bo C Ballester P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(24):7285-7295
We describe herein a detailed study of the inclusion processes of several positively charged organometallic sandwich complexes inside the aromatic cavity of the self-folding octaamide cavitand 1. In all cases, the binding process produces aggregates with a simple 1:1 stoichiometry. The resulting inclusion complexes are not only thermodynamically stable, but also kinetically stable on the (1)H NMR spectroscopy timescale. The binding constants for the inclusion complexes were determined by different titration techniques. We have also investigated the kinetics of the binding process and the motion of the metallocenes included in the aromatic cavity of the host. Using DFT-based calculations, we have evaluated the energies of a diverse range of potential binding geometries for the complexes. We then computed the proton chemical shifts of the included guest in each one of the binding geometries. The agreement between the averaged computed values and the experimentally determined chemical shifts clearly supports the proposed binding geometries that we assigned to the inclusion complexes formed in solution. The combination of experimental and theoretical results has allowed us to elucidate the origins of the distinct features detected in the complexation process of the different guests, as well as their different motions inside the host. 相似文献
998.
Magali Boutonnet Sara Lgdberg Erik Elm Svensson 《Current Opinion in Colloid & Interface Science》2008,13(4):270-286
This paper reviews the use of microemulsions, especially the water-in-oil (w/o) microemulsions, for preparation of nanoparticles that are employed as catalyst components in heterogeneous catalytic reactions. The objective is to show the growing interest of using microemulsions in the preparation of different types of materials such as metals, single metal oxides or mixed metal oxides with a broad range of application in heterogeneous catalysis and also in electrocatalysis. In most cases, the catalytic material showed improved catalytic properties as a result of the special synthesis environment created by the microemulsions. Still, research is needed for a better understanding of such beneficial effects. In addition, this method needs improvements in order to produce, in an environmentally friendly way, a suitable amount of material for use in industrial-scale catalytic processes. 相似文献
999.
Ning Nan Erik W. Johnston Judith S. Olson 《Computational & Mathematical Organization Theory》2008,14(2):57-83
In studies about office arrangements that have individuals working from remote locations, researchers usually hypothesize
advantages for collocators and disadvantages for remote workers. However, empirical findings have not shown consistent support
for the hypothesis. We suspect that there are unintended consequences of collocation, which can offset well-recognized advantages
of being collocated. To explain these unintended consequences, we developed a multi-agent model to complement our laboratory-based
experiment. In the lab, collocated subjects did not perform better than the remote even though collocators had faster communication
channels and in-group favor towards each other. Results from the multi-agent simulation suggested that in-group favoritism
among collocators caused them to ignore some important resource exchange opportunities with remote individuals. Meanwhile,
communication delay of remote subjects protected them from some falsely biased perception of resource availability. The two
unintended consequences could offset the advantage of being collocated and diminish performance differences between collocators
and remote workers. Results of this study help researchers and practitioners recognize the hidden costs of being collocated.
They also demonstrate the value of coupling lab experiments with multi-agent simulation.
相似文献
Judith S. OlsonEmail: |
1000.