Model studies of the optical rotation,and theoretical determination of its sign for β‐pinene and trans‐pinane

We have carried out extensive studies on the basis set dependence of the calculated specific optical rotation (OR) in molecules at the level of the time–dependent Hartree–Fock and density functional approximations. To reach the limits of the basis set saturation, we have devised an artificial model, the asymmetrically deformed (chiral) methane (CM) molecule. This small system permits to use basis sets which are prohibitively large for real chiral molecules and yet shows all the important features of the basis set dependence of the OR values. The convergence of the OR has been studied with n‐aug‐cc‐pVXZ basis sets of Dunning up to the 6–ζ. In a parallel series of calculations, we have used the recently developed large polarized (LPolX) basis sets. The relatively small LPolX sets have been shown to be competitive to very large n‐aug‐cc‐pVXZ basis sets. The conclusions reached in calculations of OR in CM concerning the usefulness of LPolX basis sets have been further tested on (S)‐methyloxirane and (S)‐fluoro‐oxirane. The smallest set of the LPolX family (LPol–ds) has been found to yield OR values of similar quality as those obtained with much larger Dunning's aug‐cc‐pVQZ basis set. These results have encouraged us to carry out the OR calculations with LPol–ds basis sets for systems as large as β‐pinene and trans‐pinane. In both cases, our calculations have lead to the correct sign of the OR value in these molecules. This makes the relatively small LPol–ds basis sets likely to be useful in OR calculations for large molecules. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Surface-enhanced Raman scattering (SERS) activity of Ag, Au and Cu nanoclusters on TiO2-nanotubes/Ti substrate

Tubular arrays of TiO₂ nanotubes (ranging in diameter from 40 to 110 nm) on a Ti substrate were used as a support for Ag, Au or Cu deposits obtained by the sputter deposition technique, where the amount of metal varied from 0.01 to 0.2 mg/cm². Those composite supports were intended for surface-enhanced Raman scattering (SERS) investigations. Composite samples were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured at different cathodic potentials ranging from −0.2 down to −1.2 V after the pyridine had been adsorbed on the metal-covered TiO₂ nanotube/Ti substrates. In addition, SERS spectra on a bulk standard activated Ag, Au and Cu substrates were also measured. The SERS activity of the composite samples was strongly dependent on the amount of metal deposit, e.g. at and above 0.06 mg Ag/cm², the intensity of SERS signal was even higher than that for the Ag reference substrate. The high activity of these composites is mainly a result of their specific morphology. The high SERS sensitivity on the surface morphology of the substrate made it possible to monitor very small temporal changes in the Ag metal clusters. This rearrangement was not detectable with microscopic (SEM) or microanalytical (AES) methods. The SERS activity of Au or Cu clusters was distinctly lower than those of Ag. The spectral differences exhibited by the three kinds of composites as compared to the reference metal samples are discussed.     

Holomorphic mappings preserving Minkowski functionals

We show that the equality _m1(f(x))=_m2(g(x))$m_1\left(f\left(x\right)\right)=m_2\left(g\left(x\right)\right)$ for x$x$ in a neighborhood of a point a$a$ remains valid for all x$x$ provided that f$f$ and g$g$ are open holomorphic maps, f(a)=g(a)=0$f\left(a\right)=g\left(a\right)=0$ and _m1,_m2$m_1,m_2$ are Minkowski functionals of bounded balanced domains. Moreover, a polynomial relation between f$f$ and g$g$ is obtained.     

Generalized entropy in expanded semigroups and in algebras with neutral element

The complex product of (non-empty) subalgebras of a given algebra from a variety \(\mathcal{V}\) is again a subalgebra if and only if the variety \(\mathcal{V}\) has the so-called generalized entropic property. This paper is devoted to algebras with a neutral element or with a semigroup operation. We investigate relationships between the generalized entropic property and the commutativity of the fundamental operations of the algebra. In particular, we characterize the algebras with a neutral element that have the generalized entropic property. Furthermore, we show that, similarly as for n-monoids and n-groups, for inverse semigroups, the generalized entropic property is equivalent to commutativity.     

On Hidden Markov Processes with Infinite Excess Entropy

We investigate stationary hidden Markov processes for which mutual information between the past and the future is infinite. It is assumed that the number of observable states is finite and the number of hidden states is countably infinite. Under this assumption, we show that the block mutual information of a hidden Markov process is upper bounded by a power law determined by the tail index of the hidden state distribution. Moreover, we exhibit three examples of processes. The first example, considered previously, is nonergodic and the mutual information between the blocks is bounded by the logarithm of the block length. The second example is also nonergodic but the mutual information between the blocks obeys a power law. The third example obeys the power law and is ergodic.     

Microwave-assisted Cannizzaro reaction—Optimisation of reaction conditions

The microwave-assisted Cannizzaro reaction was studied in order to develop fully reproducible synthetic protocols for transformation of aldehydes to carboxylic acid and alcohols. Optimised were the following process parameters: power, temperature, and time. Aromatic, heteroaromatic and aliphatic aldehydes were used in the studies. It was found that furfural, thiophene-2-carbaldehyde, pyridinecarboxaldehyde and aromatic aldehydes react under mild conditions, while 1-methyl-pyrrole-2-carboxaldehyde derivatives and aliphatic aldehydes require more drastic reaction conditions and a longer exposure time to microwave radiation.     

Low-Temperature TLC-MS of Essential Oils from Five Different Sage (Salvia) Species

JPC – Journal of Planar Chromatography – Modern TLC - In a previous paper we discussed the possibility of fractionating the essential oils of different sage species by low-temperature...     

Thermal properties of compressed expanded graphite: photothermal measurements

The thermal diffusivity and the thermal conductivity of compressed expanded graphite (CEG) samples were investigated by photothermal measurements in two geometries differing by a place of temperature disturbance detection. This disturbance can be detected on a surface opposite to the one at which the disturbance was generated (rear detection) or on the same surface (front detection). A measurement based on the rear detection allowed us to determine the effective thermal diffusivity of the sample, while the method with front detection gives the possibility of analysis of homogeneity of the sample. It is shown that the thermal diffusivity of CEG strongly depends on its apparent density. Moreover, CEG samples reveal anisotropy of the thermal properties. The thermal diffusivity in the direction parallel to the compacting axis is lower than the one in the direction perpendicular to it. The parallel thermal diffusivity decreases with growing apparent density, while the perpendicular thermal diffusivity significantly grows when the apparent density grows. The perpendicular thermal conductivity exhibits the same behavior as the perpendicular thermal diffusivity. The parallel thermal conductivity slightly grows with growing density and then reaches a plateau. The anisotropy of CEG samples grows with growing apparent density and vanishes for low-density samples. The photothermal measurement with front signal detection revealed that the CEG samples are non-homogeneous in the direction of the compacting axis and can be modeled by a two-layer system.     

Prediction of losses in the flow through the last stage of low‐pressure steam turbine

In this paper, the numerical modelling of the flow through the low‐pressure steam turbine last stage was presented. On the basis of predicted wet steam flow‐field, the aerodynamic as well as thermodynamic losses were estimated. For calculations of the wet steam steady flow‐field three numerical methods were employed. The first method was a streamline curvature method (SCM). The commercial CFD code (CFX‐TACflow) and an in‐house code, both solving the 3‐D RANS equations, were the next two methods. In the wet steam region, by means of all three methods, the equilibrium flow was modelled. Additionally, the in‐house CFD code was used for modelling of the non‐equilibrium steam condensing flow. In this work, the comparison of the cascade loss coefficient for stator and rotor and selected flow parameters for the stage were presented, compared and discussed. Copyright © 2006 John Wiley & Sons, Ltd.