High-pressure in situ 129Xe NMR spectroscopy and computer simulations of breathing transitions in the metal-organic framework Ni2(2,6-ndc)2(dabco) (DUT-8(Ni))

Recently, we have described the metal-organic framework Ni(2)(2,6-ndc)(2)(dabco), denoted as DUT-8(Ni) (1) (DUT = Dresden University of Technology, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane). Upon adsorption of molecules such as nitrogen and xenon, this material exhibits a pronounced gate-pressure effect which is accompanied by a large change of the specific volume. Here, we describe the use of high-pressure in situ (129)Xe NMR spectroscopy, i.e., the NMR spectroscopic measurements of xenon adsorption/desorption isotherms and isobars, to characterize this effect. It appears that the pore system of DUT-8(Ni) takes up xenon until a liquid-like state is reached. Deeper insight into the interactions between the host DUT-8(Ni) and the guest atom xenon is gained from ab initio molecular dynamics (MD) simulations. van der Waals interactions are included for the first time in these calculations on a metal-organic framework compound. MD simulations allow the identification of preferred adsorption sites for xenon as well as insight into the breathing effect at a molecular scale. Grand canonical Monte Carlo (GCMC) simulations have been performed in order to simulate adsorption isotherms. Furthermore, the favorable influence of a sample pretreatment using solvent exchange and drying with supercritical CO(2) as well as the influence of repeated pore opening/closure processes, i.e., the "aging behavior" of the compound, can be visualized by (129)Xe NMR spectroscopy.     

High-resolution imaging of inhomogeneities in superconducting tunnel junctions by scanning with a modulated electron beam

A two-dimensional image of spatial structures within a superconducting tunnel junction can be obtained by scanning the current-biased junction with an electron beam and detecting the voltage change. The resolution of this imaging technique is governed by the thermal-healing length which describes the spatial diffusion of the beam energy through the superconducting film. Due to the thermal skin efect this resolution can be improved remarkably by high-freqency modulation of the beam intensity and synchronous signal detection.     

Enantioseparation of four-membered rings by gas chromatography; an overview

The separation of enantiomers by gas chromatography on a chiral stationary phase is stored and conveniently retrieved in the molecular database Chirbase/GC. According to the present information content (version 3/96), a great variety of analytes has been published in several hundred journals. A selected review is given on 364 enantiomer separations of 102 different molecules containing at least one four-membered saturated carbocyclic ring. Factors determining the degree of enantioseparation are outlined and analyzed. Received: 16 November 1996 / Revised: 17 April 1997 / Accepted: 30 April 1997     

Birnbaum‐Saunders autoregressive conditional range model applied to stock index data

This article proposes a new approach to the conditional autoregressive range (CARR) model using the Birnbaum‐Saunders (BS) distribution. The model aims to develop volatility clustering, which incorporates extreme fluctuations, using a time‐varying evolution of the range process called the BSCARR model. Furthermore, diagnosis analysis tools for diagnosis analysis were developed to evaluate the goodness of fit, such as residual analysis, global influence measures based on Cook's distance, and local influence analysis. For illustrative purposes, three real financial market indices are analyzed. A comparison with classical CARR models was also carried out in these examples. The results indicated that the proposed model outperformed some existing models in the literature, especially a recent CARR model based on the gamma distribution even under the presence of atypical cases (observed values).