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Analytical and Bioanalytical Chemistry - Es wird eine neue extraktive Trennungsmethode für Uran beschrieben. Mit Hilfe einer Lösung von Triphenylarsinoxid in Chloroform lassen sich...  相似文献   
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The structural organization, catalytic function, and electronic properties of cysteamine monolayers on Au(111) have been addressed comprehensively by voltammetry, in situ scanning tunneling microscopy (STM) in anaerobic environment, and a priori molecular dynamics (MD) simulation and STM image simulation. Two sets of voltammetric signals are observed. One peak at -(0.65-0.70) V (SCE) is caused by reductive desorption of cysteamine. The other signal, at -(0.25-0.40) V consists of a peak doublet. The pH dependence of the latter suggests that the origin is catalytic dihydrogen evolution. The doublet feature is indicative of two distinct cysteamine configurations. Cysteamine monolayer formation from initial nucleation to a highly ordered phase has been successfully observed in real time using oxygen-free in situ STM. Random cellular patterns, disordered adlayer formation accompanied by high step edge mobility, and ultimately a highly ordered (square root 3 x 4) R30 degrees lattice are observed sequentially. Pits are formed due to enclosure of the mobile edges during the adsorption process. In the highly ordered cysteamine layer, each unit has two spots with apparent 0.6 A height difference in STM images. The coverage 5.7 +/- 0.1 x 10(-10) mol cm(-2) determined by voltammetry supports that the spots represent two individual cysteamine molecules. A priori MD and density functional simulations hold other clues to the image interpretation and indicate that the NH(3)(+) groups dominate the tunneling contrast. A wide range of interface structures, showing variations in the sulfur binding site and orientation, gauche and trans conformers, and especially hydrogen-bonding interactions, are examined, from which it is concluded that the adsorbate structure is controlled by interactions with the solvent rather than with the substrate.  相似文献   
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An algebraic Kekulé structure of a benzenoid hydrocarbon is obtained from an ordinary Kekulé structure by inscribing into each hexagon the number of pi-electrons which (according to this Kekulé structure) belong to this hexagon. We show that in the case of catafusenes, there is a one-to-one correspondence between ordinary and algebraic Kekulé structures. On the other hand, in the case of perifusenes, one algebraic Kekulé structure may correspond to several ordinary Kekulé structures.  相似文献   
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Fluorescence has been the preferred choice for data quantification in biomedical microarray formats since their earliest days. As much as the formats have grown and evolved over the years, the methods in optical analysis have become ever more sophisticated and complex in order to produce more and better output. This review will provide an insight into the most common methods and the state-of-the-art of all areas in microarray fluorescence analysis. Starting with an overview on microarray formats with a focus on their demands on the readout, the most common and useful organic fluorescent stains are discussed before proceeding on to other approaches; the use of semiconductor nanocrystals (quantum dots), polymer and silica nanoparticles and fluorescent proteins. Ways to enhance the intrinsically low signal on biochips have become increasingly important as they offer a sound approach towards the detection of low concentration sample content. The three main categories are presented: amplification using DNA, enzymes, and dendrimers. As much diversity as on the microarrays themselves can be found at the detection device. Standard optical microarray detectors, and non-standard methods using fluorescence anisotropy, fluorescence lifetime imaging (FLIM) and fluorescence resonance energy transfer (FRET), and their advantages and disadvantages are discussed.  相似文献   
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Our two original approaches, the first based on the topological (connectivity) index 3χv and the second based on the model of overlapping spheres (OS), were applied for the estimation of stability constants of copper(II) complexes (CuL) with ethylenediamines (N = 14) and diethylenetriamines (N = 8), and mixed complexes (CuLA) of amino acids and diethylenetriamines (N = 18). The stability constants of the ethylenediamine complexes were predicted “indirectly” from calibration models developed on diethylenetriamines and vice versa, and also by a more direct method using the leave-one-out procedure of cross validation (cv). By averaging all the estimates, stability constants were reproduced with a rms error of 0.56 and 0.43 log K units for diethylenetriamines and ethylenediamines, respectively.  相似文献   
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A novel general property of theS- andT-isomers (a concept which has been introduced and elaborated elsewhere1, 2) of alternant hydrocarbons is demonstrated, namely that due to the HMO total -electron energy theS-isomer should always be more stable than theT-isomer. Some other classes of conjugated isomers are also constructed, for which similar inequalities are derived.
Topologischer Effekt bei MO-Energien, 4. Mitt.: Die -Elektronen-Gesamtenergie vonS- undT-Isomeren
Zusammenfassung Es wird allgemein gezeigt, daß bei einemS-T-Isomerenpaar (beschrieben in1, 2) eines alternierenden Kohlenwasserstoffes infolge der HMO -Elektronen-Gesamtenergie dasS-Isomere stets stabiler sein sollte als dasT-Isomere. Weitere Klassen konjugierter Isomere werden konstruiert und ähnliche Ungleichungen angegeben.
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