General application of jäntti's method for the fast calculation of sorption equilibrium

On the basis of a molecular model for adsorption kinetics Jäntti introduced a method to calculate equilibriums shortly after a change of the pressure of the sorptive gas. In the present paper we show that this method is useful in many more situations than those intended originally.     

Application of jäntti's method to volumetric adsorption measurements

Jäntti introduced a method to calculate the adsorption equilibrium by measuring the actual adsorbed amount three times after a change to the gas pressure. By this method the experimental time for adsorption measurement can be considerably shortened. The procedure was developed for use in adsorption measurements where the adsorbed masses are directly measured with a balance. In the present paper we will demonstrate that the method is particularly useful in volumetric (manometric) measurements.     

Estimation of the dimensions of nano-capillaries from gas adsorption data

A new approach is presented to determine the dimensions of cylindrical nanopores from adsorption measurements.     

Exploring the origins of the power-law properties of energy landscapes: An egg-box model

Multidimensional potential energy landscapes (PELs) have a Gaussian distribution for the energies of the minima, but at the same time the distribution of the hyperareas for the basins of attraction surrounding the minima follows a power-law. To explore how both these features can simultaneously be true, we introduce an “egg-box” model. In these model landscapes, the Gaussian energy distribution is used as a starting point and we examine whether a power-law basin area distribution can arise as a natural consequence through the swallowing up of higher-energy minima by larger low-energy basins when the variance of this Gaussian is increased sufficiently. Although the basin area distribution is substantially broadened by this process, it is insufficient to generate power-laws, highlighting the role played by the inhomogeneous distribution of basins in configuration space for actual PELs.     

Oscillator spacing and the probability for the recoilless Λ-production in nuclei

The relative contribution of the recoilless and quasifreeΛ-production in the (K^?,π^?) strangeness exchange reaction in nuclei is estimated by using the nuclear Debye-Waller factor. The expressions for theΛ-oscillator spacing ?ω_Λ needed for such an estimate are derived by means of procedures which lead to quite simple formulae for ?ω_Λ as function of the mass number and are useful in obtaining improved results.     

Calibration unit for micro-anemometers at very low air velocities

Commercially available anemometers generally are used at air velocities above the cm/s range. The present contribution deals with a micro-anemometer developed for measuring air velocities in the cm/s range. For the calibration at these low velocities a calibration unit has been built which creates air velocities in this range with an accuracy of the order of one percent.     

Sources of Error in Sorption and Density Measurements

In sorption measurements, volumetric or gravimetric procedures are commonly used to determine the amount adsorbed. At low pressures, thermomolecular flow and pressure differences according to Knudsen's law disturb measurements. In volumetry, calibration of the dead space is required; in gravimetry, the influence of buoyancy has to be taken into account. In both cases, adsorption of the calibrating gas, usually helium, may disturb the measurements [1]. From the calibration measurements, the density of the sample can in principle be calculated. However, it has been observed in many experiments that its value depends on the calibrating gas. This revised version was published online in July 2006 with corrections to the Cover Date.     

A new strategy for the stereoselective synthesis of unnatural α-amino acids

A new method for the synthesis of racemic non-proteinogenic α-amino acids has been developed, which involves (i) hetero-Diels-Alder addition of ethyl 2-nitrosoacrylate to electron rich alkenes such as enol ethers, enamines and allylsilanes, (ii) NaCNBH₃ reduction of the CN bond in the oxazines thus generated, the stereochemistry of the products being controlled by epimerisation of the thermodynamically less stable isomer to the more stable one, (iii) protection of the N-H group as N-Boc and (iv) finally, N-O bond cleavage of both free and protected products to give proline or bis-homoserine derivatives, respectively. An example with concomitant reduction of the carboxylate group, resulting in the formation of the respective amino alcohol is reported. Applying this methodology to a homochiral enol ether, the protected parent d-proline was prepared in enantiomerically pure form, whereas the asymmetric synthesis of the respective bis-homoserine was unsuccessful.     

Preferential attachment during the evolution of a potential energy landscape

It has previously been shown that the network of connected minima on a potential energy landscape is scale-free, and that this reflects a power-law distribution for the areas of the basins of attraction surrounding the minima. Here, the aim is to understand more about the physical origins of these puzzling properties by examining how the potential energy landscape of a 13-atom cluster evolves with the range of the potential. In particular, on decreasing the range of the potential the number of stationary points increases and thus the landscape becomes rougher and the network gets larger. Thus, the evolution of the potential energy landscape can be followed from one with just a single minimum to a complex landscape with many minima and a scale-free pattern of connections. It is found that during this growth process, new edges in the network of connected minima preferentially attach to more highly connected minima, thus leading to the scale-free character. Furthermore, minima that appear when the range of the potential is shorter and the network is larger have smaller basins of attraction. As there are many of these smaller basins because the network grows exponentially, the observed growth process thus also gives rise to a power-law distribution for the hyperareas of the basins.