Possibilities and limitations of fast GC with narrow-bore columns

In this work, two narrow-bore capillary columns with different internal diameters (I.D.) 0.15 mm (15 m length, 0.15 microm film thickness) and 0.10 mm (10 m length, 0.10 microm film thickness) with the same stationary phase (5% diphenyl 95% dimethylsiloxane), phase ratio and separation power were compared with regard to their advantages, practical limitations and applicability in fast GC on commercially available instrumentation. The column comparison concerns fast GC method development, speed and separation efficiency, the sample transfer into the column utilizing split and splitless inlet, sample capacity, detection (analysing compounds of a wide range of polarities and volatilities--even n-alkanes C16-C28 and selected pesticides) and ruggedness (in the field of ultratrace analysis of pesticide residues in real matrix). Under conditions corresponding to speed/separation efficiency trade-off 0.10 mm I.D. versus 0.15 mm I.D. column provides a speed gain of 1.74, but all other parameters investigated were better for the 0.15 mm I.D. column concerning more efficient sample transfer from inlet to the column using splitless injection, no discrimination with split injection. Better sample capacity (three times higher for the 0.15 mm than for the 0.10 mm I.D. column) resulted in improved ruggedness and simpler fast GC-MS method development.     

Functional liquid crystal films selectively recognize amine vapours and simultaneously change their colour

During recent years, cholesteric liquid crystals have found only a few applications, one of them being temperature detection; in this study, however, we intend to show that the combination of cholesteric liquid crystals and molecules with a trifluoroacetyl function can be applied to optically detect amine vapours.     

Classical bifurcation at the transition from Rabi to Josephson dynamics

We report on the experimental demonstration of the internal bosonic Josephson effect in a rubidium spinor Bose-Einstein condensate. The measurement of the full time dynamics in phase space allows the characterization of the theoretically predicted π-phase modes and quantitatively confirms analytical predictions, revealing a classical bifurcation. Our results suggest that this system is a model system which can be tuned from classical to the quantum regime and thus is an important step towards the experimental investigation of entanglement generation close to critical points.     

Weak convergence of Galerkin approximations for fractional elliptic stochastic PDEs with spatial white noise

The numerical approximation of the solution to a stochastic partial differential equation with additive spatial white noise on a bounded domain is considered. The differential operator is assumed to be a fractional power of an integer order elliptic differential operator. The solution is approximated by means of a finite element discretization in space and a quadrature approximation of an integral representation of the fractional inverse from the Dunford–Taylor calculus. For the resulting approximation, a concise analysis of the weak error is performed. Specifically, for the class of twice continuously Fréchet differentiable functionals with second derivatives of polynomial growth, an explicit rate of weak convergence is derived, and it is shown that the component of the convergence rate stemming from the stochasticity is doubled compared to the corresponding strong rate. Numerical experiments for different functionals validate the theoretical results.     

Self-affine convex polygons

A polygon in ${{\mathbb R}^2}$ is called self-affine if it can be dissected into k ≥ 2 affine images of itself. Self-affine convex polygons have at most five vertices. Triangles are trivially self-affine. It is shown that every convex quadrangle is self-affine, whereas only some, but not all convex pentagons are self-affine.     

Lattice wave emission from moving cracks

Antiplane shear cracks moving in square lattices have been studied in a molecular dynamics simulation. They become unstable when a critical stress intensity at the tip is reached. Within picoseconds they accelerate to steady state velocity, which can be supersonic or not, depending on the interatomic potential. If the surface energy is low, they become supersonic; if the surface energy is high, they reach only subsonic speeds before the crystal reaches the theoretical shear strength. A simple modification of the interatomic potential switches the crystal behaviour from brittle to ductile, substituting dislocations to daughter cracks. The steady state velocities are the same, whether the model crystal is brittle or ductile. The steady state velocity is a function of the applied stress, not the stress intensity.     

Predicting Mole‐Fraction‐Dependent Dissociation for Weak Acids

We demonstrate for formic and acetic acid dissolved in water as examples that the binary quantum cluster equilibrium (bQCE) approach can predict acid strengths over the whole range of acid concentrations. The acid strength increases in a complex rather than a simple way with increasing mole fraction of the acid from 0 to 0.7, reflecting the complex interplay between the dissociated ions or conjugate bases available as compared to the acid and water molecules. Furthermore, our calculated ion concentrations meet the experimental maximum of the conductivity with excellent agreement for acetic acid and satisfactorily for the formic acid/water mixture. As only a limited number of simple quantum‐chemical calculations are required for the prediction, bQCE is clearly a valuable approach to access these quantities also in non‐aqueous solutions. It is a highly valuable asset for predicting ionization processes in highly concentrated solutions, which are relevant for biological and chemical systems, as well as technological processes.     

Cationic ruthenium complex of the formula [RuCl(2,6-diacetylpyridine)(PPh3)2]BArF and its catalytic activity in the formation of enol esters

A new ruthenium 2,6-diacetylpyridine complex was synthesized and applied in the atom-economic synthesis of enol esters through Markovnikov-directed addition of carboxylic acids to terminal alkynes. The ruthenium complex [RuCl(dap)(PPh₃)₂]⁺BArF^? was synthesized from [RuCl₂(PPh₃)₂] and the corresponding ligand 2,6-diacetylpyridine (dap). The complex was characterized structurally. The new ruthenium complex was utilized under ambient conditions as a catalyst in the Markovnikov addition of carboxylic acids to terminal alkynes to afford the corresponding enol esters in 93% to 52% isolated yields (85?°C, 16?h reaction time, 1?mol% catalyst loading).