The BV-capacity in metric spaces

We study basic properties of the BV-capacity and Sobolev capacity of order one in a complete metric space equipped with a doubling measure and supporting a weak Poincaré inequality. In particular, we show that the BV-capacity is a Choquet capacity and the Sobolev 1-capacity is not. However, these quantities are equivalent by two sided estimates and they have the same null sets as the Hausdorff measure of codimension one. The theory of functions of bounded variation plays an essential role in our arguments. The main tool is a modified version of the boxing inequality.     

Stable spirocyclic neutral radicals: aluminium and gallium boraamidinates

Stable dark red (M = Al) or dark green (M = Ga) neutral radicals {[PhB(mu-NtBu)2]2M} are obtained by the oxidation of their corresponding anions with iodine, and EPR spectra supported by DFT calculations show that the spin density is equally delocalized over all four nitrogen atoms in these spiroconjugated systems.     

Status of the hard X‐ray microprobe beamline ID22 of the European Synchrotron Radiation Facility

The ESRF synchrotron beamline ID22, dedicated to hard X‐ray microanalysis and consisting of the combination of X‐ray fluorescence, X‐ray absorption spectroscopy, diffraction and 2D/3D X‐ray imaging techniques, is one of the most versatile instruments in hard X‐ray microscopy science. This paper describes the present beamline characteristics, recent technical developments, as well as a few scientific examples from recent years of the beamline operation. The upgrade plans to adapt the beamline to the growing needs of the user community are briefly discussed.     

Limitations in cooling electrons using normal-metal-superconductor tunnel junctions

We demonstrate both theoretically and experimentally two limiting factors in cooling electrons using biased tunnel junctions to extract heat from a normal metal into a superconductor. First, when the injection rate of electrons exceeds the internal relaxation rate in the metal to be cooled, the electrons do not obey the Fermi-Dirac distribution, and the concept of temperature cannot be applied as such. Second, at low bath temperatures, states within the gap induce anomalous heating and yield a theoretical limit of the achievable minimum temperature.     

Overpressured layer chromatography in comparison with thin-layer and high-performance liquid chromatography for the determination of coumarins with reference to the composition of the mobile phase

The retention behaviour of fifteen closely related coumarins in normal-phase overpressured layer chromatography (OPLC) was studied with the aim of comparing the retentions with those in normal-phase thin-layer chromatography (TLC) and high-performance liquid chromatography (HPLC) when optimization of the mobile phase was carried out according to the PRISMA system. The mobile phase optimization was carried out on TLC plates in unsaturated chambers. The resulting mobile phases were transposed to off-line, non-equilibrated OPLC and further to HPLC. The retention in TLC was measured at 37 selectivity points and in OPLC and HPLC at 13 points. Capacity factors (k′) and separation factors () were calculated in order to study the retention behaviour in the different systems. Two- and three-dimensional evaluations of k′ against selectivity points showed similar retention behaviours for the coumarins in TLC, OPLC and HPLC. The values for TLC, OPLC and HPLC showed similar patterns in the three-dimensional evaluations. The retention behaviour at different solvent strengths was also examined. According to quadratic regression, k′ showed a dependence on the change in solvent strength. OPLC, which can be considered as a “planar column” technique, and TLC are closely related methods, whereas HPLC shows a different behaviour in the elution process with regard to solvent strength.     

Mono‐ and Bis(imidazolidinium ethynyl) Cations and Reduction of the Latter To Give an Extended Bis‐1,4‐([3]Cumulene)‐p‐carboquinoid System

An extended π‐system containing two [3]cumulene fragments separated by a p‐carboquinoid and stabilized by two capping N‐heterocyclic carbenes (NHCs) has been prepared. Mono‐ and bis(imidazolidinium ethynyl) cations have also been synthesized from the reaction of an NHC with phenylethynyl bromide or 1,4‐bis(bromoethynyl)benzene. Cyclic voltammetry coupled with synthetic and structural studies showed that the dication is readily reduced to a neutral, singlet bis‐1,4‐([3]cumulene)‐p‐carboquinoid as a result of the π‐accepting properties of the capping NHCs.     

Die oxydative Bromierung bei der Bestimmung der ?pfels?ure und der Asparagins?ure

Zusammenfassung Die Identität des aus Äpfelsäure — wahrscheinlich auch aus Asparaginsäure und Tyrosin — durch bromierende Permanganatoxydation entstehenden 2,4-Dinitrophenylhydrazinderivats mit sowohl aus Glyoxal als auch aus Dibromacetaldehyd hergestelltem Glyoxal-2,4-dinitrophenylosazon wurde festgestellt. Bei der Reaktion fungiert Dibromacetaldehyd als Zwischenprodukt.Auf Grund dieser Reaktion ist die Mikrobestimmungsmethode der Äpfelsäure vonPucher, Vickery undWakeman bearbeitet worden, die von A. A.Arhimo auch auf Asparaginsäure angewendet worden ist.     

Two phase transitions of poly(N-isopropylacrylamide) brushes bound to gold nanoparticles

The thermally induced phase transition of the poly(N-isopropylacrylamide) (PNIPAM) brush covalently bound to the surface of the gold nanoparticles was studied using high-sensitivity microcalorimetry. Two types of PNIPAM monolayer protected clusters (MPCs) of gold nanoparticles were employed, denoted as the cumyl- and the cpa-PNIPAM MPCs, bearing either a phenylpropyl end group or a carboxyl end group on each PNIPAM chain, respectively. The PNIPAM chains of both MPCs exhibit two separate transition endotherms; i.e., the first transition with a sharp and narrow endothermic peak occurs at lower temperature, while the second one with a broader peak occurs at higher temperature. With increase of the MPC concentration, the transition temperature corresponding to the first peak only slightly changes but the second transition temperature strongly shifts to lower temperature. The calorimetric enthalpy change in the first transition is much smaller than that in the second transition. The ratio of the calorimetric enthalpy change to the van't Hoff enthalpy change indicates that in the first transition PNIPAM segments show much higher cooperativity than in the second one. The investigation of pH dependence of two-phase transitions further indicates the PNIPAM brush reveals two separate transitions even with a change in interchain/interparticle association. The observations are tentatively rationalized by assuming that the PNIPAM brush can be subdivided into two zones, the inner zone and the outer zone. In the inner zone, the PNIPAM segments are close to the gold surface, densely packed, less hydrated, and undergo the first transition. In the outer zone, on the other hand, the PNIPAM segments are looser and more hydrated, adopt a restricted random coil conformation, and show a phase transition, which is dependent on both concentration of MPC and the chemical nature of the end groups of the PNIPAM chains. Aggregation of the particles, which may also affect the phase transition, is briefly discussed.     

Electronic structures and molecular properties of chalcogen nitrides Se2N2 and SeSN2

The electronic structures and molecular properties of S2N2 as well as the currently unknown chalcogen nitrides Se2N2 and SeSN2 have been studied using various ab initio and density functional methods. All molecules share a qualitatively similar electronic structure and can be primarily described as 2pi-electron aromatics having minor singlet diradical character of 6-8% that can be attributed solely to the nitrogen atoms. This diradical character is manifested in the prediction of their molecular properties, in which coupled cluster and multiconfigurational approaches, as well as density functional methods, show the best performance. The conventional ab initio methods RHF and MP2 completely fail to describe these systems. Predictions for the vibrational frequencies, IR intensities, Raman activities, and 14N, 15N, and 77Se chemical shifts, as well as singlet excitation energies of Se2N2 and SeSN2, have been made. The computed high-level spectroscopic data will be of considerable value in future efforts aimed at the preparation of the conducting polymers (SeN)x and (SeNSN)x.     

Characterisation of poly(N-isopropylacrylamide) by asymmetrical flow field-flow fractionation, dynamic light scattering, and size exclusion chromatography

Asymmetrical flow field-flow fractionation (AsFIFFF) was used to determine the hydrodynamic particle sizes, molar masses, and phase transition behaviour of various poly(N-isopropylacrylamide) (PNIPAM) samples synthesised by reversible addition--fragmentation chain transfer (RAFT) and conventional free radical polymerisation processes. The results were compared with corresponding data obtained by dynamic light scattering (DLS) and size exclusion chromatography (SEC). Agreement between the three methods was good except at higher molar masses, where the molar mass averages obtained by SEC were much lower than those obtained by AsFIFFF and light scattering. The aggregation of the polymers, which are thermally sensitive, was studied by DLS and AsFIFFF at various temperatures. In deionised water there was an abrupt change in the particle size due to phase separation at approximately equal to 32-35 degrees C. The critical temperatures determined by AsFIFFF were 3-5 degrees C higher than those obtained by DLS.