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41.
Michael Müller Prof. Dr. Markus Albrecht Verena Gossen Tanja Peters Andreas Hoffmann Prof. Dr. Gerhard Raabe Dr. Arto Valkonen Prof. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(41):12446-12453
The directionality of interaction of electron‐deficient π systems with spherical anions (e.g,. halides) can be controlled by secondary effects like NH or CH hydrogen bonding. In this study a series of pentafluorophenyl‐substituted salts with polyhalide anions is investigated. The compounds are obtained by aerobic oxidation of the corresponding halide upon crystallization. Solid‐state structures reveal that in bromide 2 , directing NH–anion interactions position the bromide ion in an η1‐type fashion over but not in the center of the aromatic ring. The same directing forces are effective in corresponding tribromide salt 3 . In the crystal, the bromide ion is paneled by four electron‐deficient aromatic ring systems. In addition, compounds 4 and 6 , which have triiodide and the rare tetraiodide dianion as anions, are described. Computational studies reveal that the latter is highly unstable. In the present case it is stabilized by the crystal lattice, for example, by interaction with electron‐deficient π systems. 相似文献
42.
Cametti M Ilander L Valkonen A Nieger M Nissinen M Nauha E Rissanen K 《Inorganic chemistry》2010,49(24):11473-11484
Ditopic salophen-UO(2) receptors 1-4 and 7 co-crystallize with tetramethylammonium (TMA) chloride and fluoride salts producing good quality crystals amenable for X-ray diffraction characterization. The arrangement of the receptor and salt units in the crystal lattice is such that tetrameric ball-shaped assemblies are formed, where an inner cluster of four TMA cations are surrounded by an outer shell of four UO(2)-bound anions. These elaborate architectures, which occur in all cases, regardless of a certain degree of structural modification on the receptors, lead to lattices that belong to non-centrosymmetric (NCS) space groups. Interestingly, the tetragonal symmetry of the tetrameric ball-shaped assemblies is either retained (I4?) or lost (R3c and I4?3d) at the lattice level, without compromising the NCS nature of the crystal lattices. The principal X-ray investigation on TMAX (X = Cl/F) co-crystals, that is, 1-(TMA)Cl, 2-(TMA)Cl, 3-(TMA)Cl, 4-(TMA)Cl, 7-(TMA)Cl, and 7-(TMA)F, is accompanied by NMR and electrospray ionization (ESI) mass spectrometry studies to gather additional insight on the modality of formation of the solid state structures observed. The important role of cation-π interactions in the receptor-salt recognition process is renewed and strengthened by comparison with NMR titration data with a novel reference compound, the salophen-UO(2) complex 8. Given the importance of NCS and polar crystalline solids in the development of functional materials, this study shows that this property can be introduced into elaborate host-guest systems, as those which assemble in the architectures described here, thus expanding its field of applicability. 相似文献
43.
Tero Tuuttila Manu Lahtinen Juhani Huuskonen Kari Rissanen 《Thermochimica Acta》2010,497(1-2):109-116
The thermal properties of twelve Janus-type dendrimers up to the second generation were evaluated by termogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Compounds consist of the dendritic bisMPA based polyester moieties, and either 3,4-bis-dodecyloxybenzoic acid, 3,5-bis-dodecyloxybenzoic acid or 3,4,5-tris-dodecyloxybenzoic acid moieties, attached to opposite sides of the pentaerythritol core. The thermal stability of the compounds was evaluated by TGA, displaying onset decomposition temperatures (Td) at around 250 °C. DSC measurements upon heating and cooling confirmed that OH terminated Janus dendrimers featuring large polarity difference in opposite sides display liquid crystalline phases with exception of 3,5-type G1 dendrimer; while acetonide terminated dendrimers displayed merely melting transitions. Dendrimers having terminal alkyl chains at positions 3,4 or 3,4,5 in aromatic moieties exhibited enantiotropic mesophases. However, the thermal behavior of the dendrimers with 3,5-substitution pattern was different: the 3,5-type G1 dendrimer exhibit a lack of mesomorphic transition, and in the case of the 3,5-type G2 dendrimer, the mesophase was absent in the first heating scan but was observed during the subsequent cooling and heating scans at the rate of 10 °C/min. 相似文献
44.
Satoshi Migita Akito Tateishi Kari Keinänen Tetsuya Haruyama 《Analytical and bioanalytical chemistry》2010,396(3):1153-1157
Bioassay models of neural functions must lend themselves to high-throughput analysis in neural drug discovery. However, smart
analysis methods for these functions have not yet been fully established. Here, we describe the development of a synapse model
for cell-based biosensing. The engineered synapse model cell expresses ionotropic glutamate receptor on its surface, like
the neural postsynaptic membrane. The advantages of the model cell are the ease of handling and reproducibility as compared
with the cultured neural cell, and it can be employed to evaluate receptor function through ion flux analysis. The agonist-induced
sodium influx was monitored as an agonist concentration-dependent increase in the observed fluorescence signal. Furthermore,
we found that our model cell enables the correction of uneven cellular signal levels using a reporter system. Our engineered
synapse model cell can be employed as a powerful tool for the screening of lead substances in pharmaceutical high-throughput
analysis. 相似文献
45.
Totti Laitinen Sara Herrero Martín Jevgeni Parshintsev Tuulia Hyötyläinen Kari Hartonen Marja-Liisa Riekkola Markku Kulmala José Luis Pérez Pavón 《Journal of chromatography. A》2010,1217(1):151-159
Organic compounds in atmospheric nanoparticles have an effect on human health and the climate. The determination of these particles is challenged by the difficulty of sampling, the complexity of sample composition, and the trace-level concentrations of the compounds. Meeting the challenge requires the development of sophisticated sampling systems for size-resolved particles and the optimization of sensitive, accurate and simple analytical techniques and methods. A new sampling system is proposed where particles are charged with a bipolar charger and size-segregated with a differential mobility analyzer. This system was successfully used to sample particles from wood pyrolysis with particle sizes 30–100 nm. Particles were analyzed by four techniques: comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry, gas chromatography–time-of-flight mass spectrometry, gas chromatography–quadrupole mass spectrometry, and aerosol mass spectrometry (aerosol MS). In the chromatographic techniques, particles were collected on a filter and analyzed off-line after sample preparation, whereas in the aerosol MS, particle analysis was performed directly from the particle source. Target compounds of the samples were polyaromatic hydrocarbons and n-alkanes. The analytical techniques were compared and their advantages and disadvantages were evaluated. The sampling system operated well and target compounds were identified in low concentrations. 相似文献
46.
Amir Averbuch Valery Zheludev Pekka Neittaanmäki Pekka Wartiainen Kari Huoman Kim Janson 《Applied Acoustics》2011,(1):22-34
We present a robust algorithm to detect the arrival of a boat of a certain type when other background noises are present. It is done via the analysis of its acoustic signature against an existing database of recorded and processed acoustic signals. We characterize the signals by the distribution of their energies among blocks of wavelet packet coefficients. To derive the acoustic signature of the boat of interest, we use the Best Discriminant Basis method. The decision is made by combining the answers from the Linear Discriminant Analysis (LDA) classifier and from the Classification and Regression Trees (CART) that is also accompanied with an additional unit, called Aisles, that reduces false alarms rate. The proposed algorithm is a generic solution for process control that is based on a learning phase (training) followed by an automatic real time detection while minimizing the false alarms rate. 相似文献
47.
Audio-frequency wave-guide models for antisymmetric dynamic stiffness of arbitrary long elastomer cylinders are presented. The locally non-mixed boundary conditions at the lateral and radial surfaces are simultaneously satisfied by using the modes corresponding to the dispersion relation for axial waves in cylinders satisfying the stress free boundary conditions at the curved radial boundaries, while the displacement conditions on the flat cylinder ends are satisfied by mode matching. The elastomer is modelled as nearly incompressible with deviatoric visco-elasticity based on a fractional derivative, standard linear solid embodying a Mittag-Leffler relaxation kernel, the main advantage being the minimum parameter number required to successfully model the material properties over a broad frequency band. The stiffness is found to depend strongly on frequency; displaying resonances and anti-resonances. The method is compared with and verified against finite element models. In addition, comparison to thin beam theories, i.e. Euler and Timoschenko theory and a simple shear model, is presented, illustrating the limitations of these models. 相似文献
48.
49.
Erick Kindt Sandra Bak Mueller Christine Castle Carine M. Boustany‐Kari 《Biomedical chromatography : BMC》2010,24(7):752-758
Biomarkers are an increasingly important constituent of the drug development process, offering the potential of increased efficiency through reduced compound attrition and earlier proof of mechanism and/or efficacy. Assays developed for compound screening that can be directly translated for clinical trials are especially valuable, but their successful adoption requires a careful balance between assay performance and implementation costs. One such ‘fit‐for‐purpose’ biomarker assay, the indirect measurement of pharmacological modulation of sphingolipid biosynthesis and disposition, is presented here. Among spingolipids, numerous ceramide species are readily detectable in different lipoprotein fractions of mammalian plasma, but their parallel quantification can be prohibitively expensive and time consuming. Ceramides differ in their fatty acid moiety, which is readily removed by hydrolysis, yielding a common sphingosine derivative, the measurement of which serves as an indicator of total ceramide. When followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for detection, robust analyte quantification becomes relatively straightforward. The practical utility of a method developed to be fit for the purpose of rapidly and quantitatively measuring treatment‐induced variations in total ceramide from hamster plasma and individual lipoprotein fractions is described. With a linear calibration range from 0.003 to 33.4 μm sphingosine, precision and accuracy error in plasma‐based quality controls spiked with ceramides was less than 15%. The specificity of the assay for ceramides was also assessed. The simplicity of the method would allow for its potential translation to other preclinical species, as well as for clinical applications in later‐stage drug development. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
50.
Kari Eloranta 《Journal of statistical physics》1994,76(5-6):1377-1398
We investigate the dynamics of ensembles of diffusive defects in one-dimensional deterministic cellular automata. The work builds on earlier results on individual random walks in cellular automata. Here we give a natural condition guaranteeing diffusive behavior also in the presence of other defects. Simple branching and birth mechanisms are introduced and prototype classes of cellular automata exhibiting weakly interacting walks capable of annihilation and coalescence are studied. Their equilibrium behavior is also characterized. The design principles of cellular automata with desired diffusive interaction properties become transparent from this analysis. 相似文献