Rime samples characterization and comparison using classical and fuzzy principal components analysis

The main objective of this paper is to introduce principal component analysis and two robust fuzzy principal component algorithms as useful tools in characterizing and comparing rime samples collected in different locations in Poland (2004–2007). The efficiency of the applied procedures was illustrated on a data set containing 108 rime samples and concentration of anions, cations, HCHO, as well as pH and conductivity. The fuzzy principal component algorithms achieved better results mainly because they are more compressible than classical PCA and very robust to outliers. For example, a three component model, fuzzy principal component analysis-first component (FPCA-1) accounts for 62.37% of the total variance and fuzzy principal component analysis-orthogonal (FPCA-o) 90.11%; PCA accounts only for 58.30%. The first two principal components explain 51.41% of the total variance in the case of FPCA-1 and 79.59% in the case of FPCA-o as compared to only 47.55% for PCA. As a direct consequence, PCA showed only a partial differentiation of rime samples onto the plane or in the space described by different combination of two or three principal components, whereas a much sharper differentiation of the samples, regarding their origin and location, is observed when FPCAs are applied.      

Synthesis and cytostatic activity of 4,7-dihydroxythioaurone derivatives. Effect of B ring substitution on the activity

Biological activity of thioaurones was not tested so far and the group constitute completely unexplored source of new molecules of pharmacological interest. We report synthesis and evaluation of cytotoxic activity of thioaurone derivatives bearing p-hydroquinone system in ring A. Their activity was found to depend strongly on substitution pattern, so eventually both the activity and pharmacokinetic parameters of the molecules could be tailored by further structural modifications.     

Ethanol production in a bioreactor with an integrated membrane distillation module

Ethanol production in a bioreactor with integrated membrane distillation (MD) module has been investigated. A hydrophobic capillary polypropylene membrane (Accurel PP V8/2 HF), with an external/internal diameter ratio, d _out/d _in = 8.6 mm/5.5 mm and pore size 0.2 μm, was used in these studies. The products (mainly ethanol and acetic acid) formed during the fermentation of sugar with Saccharomyces cerevisiae inhibited the process. These products were selectively removed from the fermentation broth by the MD process, which increased the efficiency of the conversion of sugar to alcohol from 0.45 g to 0.5 g EtOH per g of fermented sucrose. The bioreactor efficiency also increased by almost 30 %. Separation of alcohol by the MD generates a higher yield of ethanol in the permeate than in the broth. The enrichment coefficient amounted to 4-8, and depended on the ethanol concentration in the broth. The separated solutions did not wet the membrane in use for 2500 h of the MD experiments and the retention of inorganic solutes was close to 100 %.     

Synthesis of β-ketophosphonates with electron rich β-aryl groups as useful organophosphorus reagents in lignans synthesis

Investigation of the oxidation reaction of electron rich alkoxy substituted β-aryl β-hydroxyphosphonates to corresponding β-ketophosphonates, which may be utilized in syntheses of lignans with various oxidizing agents (PCC, PDC, SIBX, CAN, Oxone^®, KMNO₄/SiO₂, KMnO₄/MS 4 Å, KMnO₄/CuSO₄, KMnO₄/CuSO₄/Al₂O₃, MnO₂, CrO₃/SiO₂, H₂O₂/salen) is described. The effect of oxidants and reaction conditions on the reaction efficiency and yield was also investigated.     

Nuclear resonance vibrational spectra of five-coordinate imidazole-ligated iron(II) porphyrinates

Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate, or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200-300 cm(-1). Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with density functional theory (DFT) calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe-N(Im) vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape).     

Synthesis and characterization of two homologous series of diastereomeric 2-alkoxyphenylcarbamates

Two homologous series of racemic diastereomeric cis- and trans-(2-dimethylaminomethylcycloheptyl)-2-alkoxyphenylcarbamates with alkyl chain lengths ranging from C? to C? were synthesized by stereoselective reactions. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR and IR spectroscopy and their physico-chemical properties were characterized. The two new series of diastereomeric compounds were tested for their local anesthetic activity and parabolic relationship between the local anesthetic activity and lipophilicity was found for both cis- and trans-series. Interestingly, cis-stereoisomers exhibited higher local anesthetic activity.     

The synthesis of 3,6-diamino-2,3,4,6-tetradeoxy-dl-threo-hexopyranose derivatives,substrates for the synthesis of negamycin

Three synthetic routes to derivatives of 3,6 - diamino - 2,3,4,6 - tetradeoxy - DL - threo - hexopyranose were investigated. Addition of sodium azide in acetic acid to 6 - phthalimido - 5,6 - dihydro - 2 - pyrone gave 4-azido compound (7) of the erythro configuration. From methyl 2,4 - dideoxy - β -dl- erythro - hexopyranoside threo 4 - phthalimido - 6 - phthalimidomethyl - tetrahydro - 2 - pyrone (17) was obtained in three steps in low overall yield. Addition of sodium azide in acetic acid to butyl 6 - oxo - 2 - hydroxy - hex - 4 - enoate followed by methylation, amonolysis of the ester group, and reduction gave methyl 3,6 - diacetamido - 2,3,4,6 - tetradeoxy - α - DL - threo - hexopyranoside (26).     

Formation of the radical-cation of monomer in the photoinduced polymerization of isobutylene in the presence of SnCl4

Spectra of isobutylene with SnCl₄ were studied at the temperature of 113°K in the dark and under illumination. Radical-cations of isobutylene are formed by irradiation of the isobutylene–SnCl₄ mixture in n-heptane substantially more slowly than in the isobutylene–TiCl₄ mixture. Polymerization of isobutylene occurs after increasing the temperature up to the melting point of this mixture. The yield of polymer depends on the duration of preirradiation, while the molecular weight of polyisobutylene (M _η) does not depend on the preirradiation of reaction mixture.     

Hydrodynamics of interaction of particles (including cells) with surfaces

The study of the phenomena related to the motion of particles flowing in the proximity of the wall is pursued for purely cognitive reason as well as for some important practical purposes in various fields of technology, biology and medicine.When small spherical rigid particles move in the direction parallel to the surface their velocity is smaller than that of the fluid and depends on the ratio of the distance from the wall to the particle radius. The velocity of a particle falling down in a vertical cylinder is maximal in an eccentric position. A sphere in contact with the wall remains stationary. Translational velocity of spherical rigid particles the dimension of which are comparable to that of the tube is only slightly dependent of their lateral position. The differences in the flow parameters of deformable particles in comparison with rigid ones depend on the particle and fluid viscosity coefficient. When the particles move perpendicularly toward the wall, their velocity decreases as the particle approaches the surface. The change of particle velocity is inversely proportional to the gap.There are several theories explaining the influence of the channel diameter on the suspension viscosity (sigma phenomenon); a modern approach is based on the analysis of rheological properties of suspensions. The explanations of the Fahraeus effect (i.e. the fact that the concentration of particles flowing in a tube linking two containers are smaller than that in the containers) are based on non-uniform particle distribution in a transverse cross section and on the differences of velocities of particles and medium. The deviation of the velocity profile of a suspension of rigid particles flowing through a tube from the parabolic shape (blunting) does not depend on the flow velocity; as concerns deformable particles, however, this effect is the smaller the greater is the flow velocity.When the Reynolds number for particles is greater than 10^-3, there appears a component of particle velocity perpendicular to the streamline direction.This phenomenon is the cause of the lateral migration of particles. Neutrally buoyant rigid particles migrate to a certain concentrical region situated between the tube axis and the wall (tubular pinch region). Deformable neutrally buoyant particles migrate towards the tube axis, and deformable non-neutrally buoyant particles may move either toward the tube axis or toward the wall.In the research on the influence of the flow delimiting surface on the motion of particles in suspension a considerable progress has recently been made.However, the phenomena in this field are extremely complex. At present, two main types of approach may be distinguished. On a microscopic level direct interactions between particles and surfaces are analyzed. A macroscopic approach consists in treating particle suspension as fluid, and overall influence of the surface on its properties are studied. A comprehensive theory linking these two levels has not yet emerged.