Simultaneous confidence and prediction bands in the certification of pressure-volume curves for the pore size analysis of solids by means of mercury porosimetry

The pore size analysis of solids is widely applied in chemical industries, materials engineering, ceramic production, environmental engineering, catalysis, chromatography, nanotechnology, and many other fields. In spite of several new methods used for determining the pore size distribution of meso- and macropores [see IUPAC Recommendations of 1994], mercury porosimetry has remained one of the most popular methods employed for the characterisation of porous materials. In this paper, a new way is described for the estimation of certified pressure-volume curves from experimental curves measured by different laboratories in connection with the certification of new reference materials for a comparatively low-pressure range of mercury intrusion (<2 MPa). Simultaneous confidence and prediction bands for the certified pressure-volume curves are constructed by bootstrapping.     

Metal catalyst-free amination of meso-bromoporphyrins: an entry to supramolecular porphyrinoid frameworks

meso-Bromoporphyrins can be conveniently substituted by primary and secondary amines in a metal catalyst-free reaction which gives access to a large variety of meso-N-substituted derivatives. In some cases, considerable acceleration of this amination can be effected under microwave irradiation. The amino anchor on the porphyrin skeleton is useful for constructing novel self-assembling porphyrinoids as demonstrated by a single crystal X-ray analysis as well as stationary absorption and fluorescence spectroscopies.     

Chernoff's Theorem and Discrete Time Approximations of Brownian Motion on Manifolds

Let be a one-parameter family of positive integral operators on a locally compact space . For a possibly non-uniform partition of define a finite measure on the path space by using a) for the transition between any two consecutive partition times of distance and b) a suitable continuous interpolation scheme (e.g. Brownian bridges or geodesics). If necessary normalize the result to get a probability measure. We prove a version of Chernoff's theorem of semigroup theory and tightness results which yield convergence in law of such measures as the partition gets finer. In particular let be a closed smooth submanifold of a manifold . We prove convergence of Brownian motion on , conditioned to visit at all partition times, to a process on whose law has a density with respect to Brownian motion on which contains scalar, mean and sectional curvatures terms. Various approximation schemes for Brownian motion on are also given.      

The effect of long-range forces on the dynamics of a bar

The one-dimensional dynamic response of an infinite bar composed of a linear “microelastic material” is examined. The principal physical characteristic of this constitutive model is that it accounts for the effects of long-range forces. The general theory that describes our setting, including the accompanying equation of motion, was developed independently by Kunin (Elastic Media with Microstructure I, 1982), Rogula (Nonlocal Theory of Material Media, 1982) and Silling (J. Mech. Phys. Solids 48 (2000) 175), and is called the peridynamic theory. The general initial-value problem is solved and the motion is found to be dispersive as a consequence of the long-range forces. The result converges, in the limit of short-range forces, to the classical result for a linearly elastic medium. Explicit solutions in elementary form are given in a broad class of special cases. The most striking observations arise in the Riemann-like problem corresponding to a constant initial displacement field and a piecewise constant initial velocity field. Even though, initially, the displacement field is continuous, it involves a jump discontinuity for all later times, the Lagrangian location of which remains stationary. For some materials the magnitude of the discontinuity-jump oscillates about an average value, while for others it grows monotonically, presumably fracturing the material when it exceeds some critical level.     

Analysis of a new drug of abuse: Cathinone derivative 1‐(3,4‐dimethoxyphenyl)‐2‐(ethylamino)pentan‐1‐one

Recently, novel psychoactive drugs for human abuse such as amphetamines, phenethylamines, benzofuries, and tryptamines, cathinones have gained high popularity. These designer drugs are mainly sold via online stores as “bath salts” and are labeled “not for human consumption.” Due to the novelty of the compounds, only a little information about pharmacology, toxicology, and the long‐term damage they may cause is available. Moreover, there are only few analytical methods for their identification and analysis. Among new cathinone derivatives, 1‐(3,4‐dimethoxyphenyl)‐2‐(ethylamino)pentan‐1‐one (DL‐4662), became available via an internet shop. A sample of this compound was purchased and investigated. The first aim of our study was an identity check by NMR spectroscopy and gas chromatography with mass spectrometry. As many of the recreational drugs are chiral and are mainly sold as racemates, a further goal of our research was enantioseparation by gas chromatography with mass spectrometry and high‐performance liquid chromatography with UV detection, to prove whether DL‐4662 was traded enantiomerically pure or as racemic mixture. Both chiral separation methods showed the presence of a racemate.