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101.
Banks CE Kruusma J Moore RR Tomcík P Peters J Davis J Komorsky-Lovrić S Compton RG 《Talanta》2005,65(2):423-429
Three different electroanalytical techniques for the detection of manganese in marine sediments are evaluated. The anodic stripping voltammetry of manganese at an in situ bismuth-film-modified boron-doped diamond electrode and cathodic stripping voltammetry at a carbon paste electrode are shown to lack the required sensitivity and reproducibility whereas cathodic stripping voltammetry at a bare boron-doped diamond electrode is shown to be reliable and selective with a limit of detection, from applying a 60 s accumulation period of 7.4 × 10−7 M and a sensitivity of 0.24 A M−1. The method was used to evaluate the manganese content of marine sediments taken from Šibenik, Croatia. 相似文献
102.
2-Nitrophenylhydrazine (2-NPH) is widely used for the derivatization of carboxylic acids, aldehydes and ketones, in industrial and biological samples. These compounds react with 2-NPH to form derivatives, which are separated by high-performance liquid chromatography (HPLC) and detected with diode array detection (DAD). The UV spectra give information about the functionality of the compounds: carboxylic acid or ketone/aldehyde. Most of the eluting compounds in "known" samples are well characterised by the retention time (comparison with those of standards) of the 2-NPH derivative and their UV spectrum. The identification of different unknown 2-NPH derivatives of carboxylic acids, ketones and/or aldehydes, in industrial or biological samples, based on retention time and/or UV spectrum is not sufficient. These unknown 2-NPH compounds can be identified with on-line atmospheric pressure chemical ionisation mass spectrometry (APCI-MS) based on the molecular mass or/and the fragmentation of the derivative. A novel and specific on-line HPLC-DAD-APCI(-)-MS method is described for the determination of carboxylic acids, ketones and aldehydes, after on-line pre-column derivatization with 2-NHP. The fragmentation of different 2-NPH derivatives were investigated and the possibilities of APCI(-)-MS detection were demonstrated by the on-line identification of an unknown derivative, which turned out to be a side product between 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 2-NPH in the presence of high concentrations of a cyclic amide in the sample solution. 相似文献
103.
19F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo6Br Cl )F ]2?, n = 0 – 8 The complete system of the innersphere mixed clusters (Mo6BrCl)4+ is formed by exchange of innersphere bound Cli against outersphere bound Bra on tempering the solid [(Mo6Cl)Br] at 500°C for 16 h. After conversion with conc. HCl into (H3O)2[(Mo6BrCl)Cl] and precipitation of the outer Cla with AgBF4 in ethanol, treatment with tetrabutylammonium(TBA)fluoride yields (TBA)2 [(Mo6BrCl)F], a mixture of 22 different species. According to the sets of chemical equivalent fluorine atoms in total 55 19F nmr signals are expected, which are really observed in the high resolution 1D-19F-nmr spectrum. Using increments of chemical shifts, peak intensities and multiplet structures as well as the 2D-19F/19F-COSY spectrum the complete and unambiguous assignment of all resonances is achieved. From the measured integral intensities the distribution of the different compounds is determined, revealing statistical formation of the geometrical isomers. 相似文献
104.
Klomp D Maschmeyer T Hanefeld U Peters JA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(8):2088-2093
The mechanism of hydrogen transfer from alcohols to ketones, catalysed by lanthanide(III) isopropoxides or zeolite Beta has been studied. For the lanthanide catalysed reactions, (S)-1-phenyl-(1-(2)H(1))ethanol and acetophenone were used as case studies to determine the reaction pathway for the hydrogen transfer. Upon complete racemisation all deuterium was present at the 1-position, indicating that the reaction exclusively takes place via a carbon-to-carbon hydrogen transfer. Zeolite Beta with different Si/Al ratios was applied in the racemisation of (S)-1-phenylethanol. In this case the racemisation does not proceed via an oxidation/reduction pathway but via elimination of the hydroxy group and its re-addition. This mechanism, however, is not characteristic for all racemisation reactions with zeolite Beta. When 4-tert-butyl cyclohexanone is reduced with this catalyst, a classical MPV reaction takes place exclusively. This demonstrates that zeolite Beta has a substrate dependent reaction pathway. 相似文献
105.
H. P. Peters D. Stauffer H. P. Hölters K. Loewenich 《Zeitschrift für Physik B Condensed Matter》1979,34(4):399-408
Monte Carlo simulation and series expansion shows the radius of gyration of large clusters withs sites each to vary ass
with0.56 in two and0.47 in three dimensions at the percolation threshold, and with(d=2)0.65 and(d=3)0.53 for random lattice animals (zero concentration). Clusters up tos=100 were used. The perimeter of random animals approaches 2.8s for larges on the simple cubic lattice. Monte Carlo simulation of the Eden process (growing animals) up tos=5,000 indicates a systematic variation of about ±0.05 for the effective exponent=(s) and thus suggests that the true asymptotic exponents may be compatible with the predictions of hyper-scaling. 相似文献
106.
Marcel Sickert Harald Weinstabl Brendan Peters Xiao Hou Mark Lautens 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(20):5247-5251
A palladium‐catalyzed intermolecular cross‐coupling of two aryl iodides is reported, giving polycyclic ring systems with a high level of convergence and efficiency. 相似文献
107.
Achim Rosch 《物理学进展》2013,62(3):295-394
In this review, a detailed discussion of the behaviour of a heavy particle interacting with a Fermi sea is given. Particular emphasis is put on the issue of how strong correlations influence coherence and transport of the particle. First, we investigate the question of whether the heavy particle is a well defined quasiparticle at low temperatures. While in one dimension ( D = 1) and at a van Hove singularity in D = 2 the coherence of the particle is destroyed, the quasiparticle weight is finite in higher dimensions. The most important transport quantity is the diffusion constant or mobility of the heavy particle. We are able to describe both the well known high-temperature properties and the cross-over to the lowest temperatures in a unified approximation scheme based on a self-consistent evaluation of an effective action. Two strong-correlation effects of independent origin are discussed. The first arises if the scattering of the fermions from the heavy particle is nearly resonant, that is, if one of the scattering phase shifts δ is close to π/2. In this regime an anomalous exponent is observed in the temperature dependence of the mobility μ(T). In D = 3, for instance, the mobility is proportional to T-3/2 rather than to T-2. The second effect is a giant mass renormalization in the case of a large particle. In this situation, the low-temperature effective mass M* increases up to an exponentially large value, M* exp[c(r/λF)3], where r is the effective radius of the particle, λF the Fermi wavelength and c a non-universal constant of order one. 相似文献
108.
Mathematical deconvolution methods can separate co-eluting peaks in samples for which (chromatographic) separation fail. However, these methods often heavily rely on manual user-input and interpretation. This is not only time-consuming but also error-prone and automation is needed if such methods are to be applied in a routine manner. 相似文献
109.
Christian Schönbeck René Holm Peter Westh Günther H. Peters 《Journal of inclusion phenomena and macrocyclic chemistry》2014,78(1-4):351-361
The formation of inclusion complexes of hydroxypropylated β-cyclodextrins (CDs) with three bile salts are investigated to shed light on the role played by the hydroxypropyl (HP) substituents. The HP-chains are situated at the rim of the CD and may thus extend the hydrophobic cavity of the CD. Calorimetric titrations in a broad temperature range and molecular dynamics simulations confirm previous speculations that the HP-chains cause an increase in dehydrated nonpolar surface area upon formation of the complexes. This additional burial of nonpolar surface area, 12–16 Å2 per HP-chain according to the MD simulations, results in more negative values of ΔC p °, which are in quantitative agreement with what is expected for hydrophobic dehydration. Although these observations support the picture of an extended hydrophobic cavity, HPβCD complexes were less stable than their unsubstituted counterparts. This indicates that increased hydrophobic contacts are not always accompanied by increased binding strength. The linear dependence of ΔC p °, ΔH° and ΔS° on the number of HP-chains give rise to isoentropic and isoenthalpic temperatures at which ΔH° and ΔS° are independent of the number of HP-chains on the host CD (but depend on the type of bile salt). Interestingly, these convergence temperatures are close to what is observed for unfolding of proteins and may be a common feature of hydrophobic dehydration. 相似文献
110.
We prove that the componentwise maximum of an i.i.d. triangular array of chi-square random vectors converges in distribution,
under appropriate assumptions on the dependence within the vectors and after normalization, to the max-stable Hüsler–Reiss
distribution. As a by-product we derive a conditional limit result. 相似文献