Preliminary studies on the surface layer of starch

Characterization of the surface layer of starch powder, originated from potato or maize, was carried out applying various experimental techniques: Fourier-transformed infrared internal reflection spectroscopy (FTIR-IRS), inverse gas chromatography (IGC) and scanning electron microscopy (SEM). The main kinds of starch were studied as potential fillers for rubber and results discussed in terms of factors requiring modification to improve starch miscibility and activity towards rubber. Starch of high amylopectine content shows surface enrichment with amylose what makes crystallinity of the surface layer higher than in bulk of the material. Particles of the both kinds of starch have very smooth surface (morphological index, I_m = 0.995), highly resistant to its geometrical development. Dispersive component of the surface energy of starch was found to be similar to that of low energy polymers (γ_s^d = 32.5 mJ/m² at 23°C) and its surface to be of electron-donor character.     

The power of adaptive algorithms for functions with singularities

This is an overview of recent results on complexity and optimality of adaptive algorithms for integrating and approximating scalar piecewise r-smooth functions with unknown singular points. We provide adaptive algorithms that use at most n function samples and have the worst case errors proportional to n^−r for functions with at most one unknown singularity. This is a tremendous improvement over nonadaptive algorithms whose worst case errors are at best proportional to n⁻¹ for integration and n^−1/p for the L^p approximation problem. For functions with multiple singular points the adaptive algorithms cease to dominate the nonadaptive ones in the worst case setting. Fortunately, they regain their superiority in the asymptotic setting. Indeed, they yield convergence of order n^−r for piecewise r-smooth functions with an arbitrary (unknown but finite) number of singularities. None of these results hold for the L^∞ approximation. However, they hold for the Skorohodmetric, which we argue to be more appropriate than L^∞ for dealing with discontinuous functions. Numerical test results and possible extensions are also discussed.     

Steric control of bacteriochlorophyll ligation

The axial coordination of central Mg(2+) ion in chlorophylls is of great structural and functional importance for virtually all photosynthetic chlorophyll proteins; however, little thermodynamic data are available on the ligand binding to these pigments. In the present study, spectral deconvolution of the bacteriochlorophyll Q(X) band serves to determine the ligand binding equilibria and relationships between thermodynamic parameters of ligand binding, ligand properties, and steric interactions occurring within the pigment. On the basis of the temperature effects on coordination, DeltaH degrees, DeltaS degrees, and DeltaG degrees of binding various types of ligands (acetone, dimethylformamide, imidazole, and pyridine) to diastereoisomeric bacteriochlorophylls were derived from respective van't Hoff's plots. At ambient temperatures, only ligation by imidazole and pyridine occurs spontaneously while DeltaG degrees becomes positive for ligation by acetone and dimethylformamide, due to a relatively large entropic effect, which is dominating when the energetic effects of ligation are small. It reflects, in quantitative terms, the control of the equatorial coordination of the Mg(2+) ion via the axial coordination: a "hard" free Mg(2+) ion is made into a softer center through the coordination of tetrapyrrole. Pigment structural features have comparable effects on the energetic and entropic contributions to the difference of ligation free energy between the diastereoisomers of bacteriochlorophyll. DeltaS degrees and DeltaH degrees values are consistently lower for the S epimer, most likely due to the steric crowding between bulky substituents. The two epimers show a 5 J.mol(-1).K(-1) difference in DeltaS degrees values, regardless of the ligand type, while the difference in DeltaH degrees amounts to 1.7 kJ.mol(-1), depending on the ligand. Such steric control of ligation would relate to the partial diastereoselectivity of chlorophyll self-assembly and, in particular, the very high diastereoselectivity of the ligation of chlorophylls in photosynthetic proteins.     

An apparent critical point in binary mixtures: experimental and simulation study

We report the experimental and simulation studies for the system of nitrobenzene-cyclododecane, showing an apparent critical point, which lies in their metastable, experimentally inaccessible state, below their melting point, affecting physical and chemical properties of this system in the stable liquid phase. The nonlinear dielectric effect (NDE) was measured in the mixture of nitrobenzene with cyclododecane. The mixture has been found to show an apparent critical point which lies below the melting point, manifested as anomalous NDE behavior in the vicinity of the critical concentrations in the stable liquid phase. The melting temperature of this system was estimated using the differential scanning calorimetry method. For such a system, we also performed Monte Carlo (MC) simulations that aimed to analyze the kinds of phase transitions observed and the conditions of their occurrence in Lennard-Jones mixture. The enthalpy, configurational energy, and radial distribution function have been estimated by the MC simulation method in the N-P-T system. Immiscibility conditions according to the approach by Schoen and Hoheisel [Mol. Phys. 57, 65 (1986)] are also discussed.     

New chiral tin compounds containing the 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand

A series of tri- and tetraorganotin compounds containing the optically active 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand and tert-butyl, methyl and/or phenyl groups on the tin has been synthesized. All the novel compounds have been characterized, especially by means of the multinuclear NMR investigation, the results of which are discussed. The tin halides, as pairs of diastereoisomers in solution, crystallize in the form of one diastereoisomer. The single-crystal X-ray analysis of tin iodide 10a revealed pseudo-equatorial position of the tert-butyl group opposite to the isopropyl group. In the corresponding diastereomeric tin hydrides values of ¹J(¹H-^117/119Sn) differ significantly, suggesting a different pseudo-axial/equatorial position of the hydrogen atom.     

Numerical analysis of the states of deformation and stress in the compact tension specimen (CT)

This work presents a new method of determination of the states of stresses and strains in the compact tension specimen (CT). The numerical analysis was carried out in ANSYS/LS–DYNA programme. The Cowper–Symond's material model was applied in the computational analysis. Selected mechanical properties executed from the uniaxial tension test were used in the numerical calculations. The main aim of this paper is to determinate the influence of the dimensions and vertical notch angle of CT on the stresses and strains states. The present application allows a calculation of the states of stresses and strains in arbitrarily specimen place, and at any time of the duration of the tensile test process. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Type-II superlattice detectors for free space optics applications and higher operating temperature conditions

The utmost limit performance of interband cascade detectors optimized for the longwave range of infrared radiation is investigated in this work. Currently, materials from the III–V group are characterized by short carrier lifetimes limited by Shockley-Read-Hall generation and recombination processes. The maximum carrier lifetime values reported at 77 K for the type-II superlattices InAs/GaSb and InAs/InAsSb in a longwave range correspond to ～200 and ～400 ns. We estimated theoretical detectivity of interband cascade detectors assuming above carrier lifetimes and a value of ～1–50 μs reported for a well-known HgCdTe material. It has been shown that for room temperature the limit value of detctivity is of ～3–4×10¹⁰ cmHz^1/2/W for the optimized detector operating at the wavelength range ～10 μm could be reached.     

IR spectra of halothane–acetone complex in liquefied noble gases (Kr and Xe)

The interaction of semiconductor quantum dots and silver nanoparticles (AgNPs) with bacteriorhodopsin (BR), a membrane protein contained in the purple membrane (PM) of Halobacterium salinarum, is studied. It is shown that both types of nanoparticles are adsorbed efficiently on the surface of the purple membranes, modulating the parameters of the bacteriorhodopsin photocycle. Electrostatic interactions are found to be the main cause of the effect of nanoparticles on the bacteriorhodopsin photocycle. These results explain our earlier data on the “fixation” of the bacteriorhodopsin photocycle for protein molecules trapped after incubation of the purple membranes with silver nanoparticles near the location of the “hot spots” of the effect of surface-enhanced Raman scattering (SERS). It is demonstrated that exposure of silver nanoparticles with bacteriorhodopsin in SERS-active regions lowers the amount of bacteriorhodopsin molecules involved in phototransformations.     

Electronic Nose Differentiation between Quercus robur Acorns Infected by Pathogenic Oomycetes Phytophthora plurivora and Pythium intermedium

Identification of the presence of pathogenic oomycetes in infected plant material proved possible using an electronic nose, giving hope for a tool to assist nurseries and quarantine services. Previously, species of Phytophthora plurivora and Pythium intermedium have been successfully distinguished in germinated acorns of English oak Quercus robur L. Chemical compound analyses performed by HS-SPME/GC-MS (Headspace Solid-Phase Microextraction/Gas Chromatography–Mass Spectrometry) revealed the presence of volatile antifungal molecules produced by oak seedlings belonging to terpenes and alkanes. Compounds characteristic only of Phytophthora plurivora or Pythium intermedium were also found. Methylcarveol occurred when germinated acorns were infected with Pythium, while neophytadiene (isomer 2 and 3) occurred only when infected with Phytophthora. Moreover, isopentanol was found in acorns infected with Phytophthora, while in control, isopentyl vinyl ether was not observed anywhere else. Among the numerous volatile compounds, isopentanol only occurred in acorns infected with Phytophthora and methylcarveol in acorns infected with Pythium.