Silicon‐containing heterocyclic polymers and thin films made therefrom

Thin films, in the range of tens of micrometers thickness, have been prepared by casting onto glass plates the chloroform or N‐methylpyrrolidone solutions of polyimides or poly(imide‐amide)s containing silicon and phenylquinoxaline units in the main chain. The polymers have been synthesized by solution polycondensation reaction of aromatic diamines having preformed phenylquinoxaline rings with bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride or with a diacid chloride resulting from the reaction of this dianhydride with p‐aminobenzoic acid. The polymers were easily soluble in polar aprotic solvents and showed high thermal stability. The free‐standing films exhibited good mechanical properties with tensile strengths in the range of 48–86 MPa, tensile modulus in the range of 1.25–2.22 GPa and elongation at break in the range of 3–37%. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz were in the range of 2.94–3.08 for polyimides and 3.89–4.49 for poly(imide‐amide)s. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3062–3068, 2006     

The genesis of polyaniline nanotubes

Aniline has been oxidized with ammonium peroxydisulfate in 0.4 M acetic acid. Protons are produced in the course of oxidation and the pH decreases as the reaction proceeds. The oxidation had two subsequent phases: (1) the oxidation of the neutral aniline molecules and the initially produced low-molecular weight aniline oligomers at low acidity, followed by (2) the oxidation of the anilinium cation after the acidity became higher. The two phases of oxidation gave different products, aniline oligomers with mixed ortho- and para-coupling of aniline molecules, and polyaniline nanotubes, respectively.The aniline oligomers are produced at first at low acidity, pH > 4, some of them as rod-like crystals. The molecular weight of the oligomers has been assessed by gel-permeation chromatography to be of several thousands. The 2-3 wt.% content of sulfur in deprotonated samples suggests that the oxidation products are partly sulfonated. The oxidation of ortho-coupled anilines combined with intramolecular cyclization produces phenazine units or their blocks, as indicated by FTIR spectra. A high-molecular weight polyaniline is produced at pH < 2. The protonation of the intermediate pernigraniline form of polyaniline is a prerequisite for the polymerization.The nano-sized oligomer crystallites serve as starting templates for the nucleation of PANI nanotubes. Further growth of nanotubes proceeds by the self-organization of the phenazine units or their blocks located at the ends of the PANI chains. Polyaniline nanotubes have a typical outer diameter of 100-200 nm, with a wall thickness of 50-100 nm, an inner diameter of 0-100 nm, and a length extending to several micrometres.     

Polymerization characteristics of a dye of anthraquinone

A technical dye of the anthraquinone type was analyzed by GPC, mass spectroscopy, and elemental analysis. Along with the polymerizable component, N-[4-amino-3-methoxyanthraquinonyl-(1)] methacrylamide (I), it contained a saturated admixture, N-[4-amino-3-methoxyanthraquinonyl-(1)]-2-chloro-2-methylpropionamide (II). The homopolymerization of I was carried out, and admixture II was isolated and characterized. The copolymerization of the dye with styrene and methyl methacrylate was verified, and the retardation effect of II on the polymerization of these monomers was evaluated.     

Optical–microphysical properties of smoke haze from Siberian forest fires in summer 2012

A comprehensive experiment on the study of dynamics of optical and microphysical characteristics of submicron aerosols in the near-ground air layer was carried out in June–August of 2012 under conditions of extremely strong smoke haze originating from vast forest fires in Siberia. Variations of the spectral angular scattering coefficients and the degree of linear polarization in the visible wavelength range are studied, as well as the mass concentrations of dry fractions of aerosol and black carbon, relative content of black carbon (BC fraction), single scattering albedo, particle size distribution function, complex refractive index of the particulate matter, and parameter of condensation activity of aerosol. Peculiarities of differences between optical and microphysical characteristics of near-ground aerosol in smoke haze and under smokeless conditions are revealed. This study is important for validation of results of remote sensing of the composition of smoke haze and background atmosphere obtained from satellite data and sun photometric measurements at the Aerosol Robotic Network (AERONET).     

Processing of Particle-Stabilized Wet Foams Into Porous Ceramics

Direct foaming of colloidal suspensions is a simple and versatile approach for the fabrication of macroporous ceramic materials. Wet foams produced by this method can be stabilized by long-chain surfactants or by colloidal particles. In this work, we investigate the processing of particle-stabilized wet foams into crack-free macroporous ceramics. The processing steps are discussed with particular emphasis on the consolidation and drying process of wet foams. Macroporous alumina ceramics prepared using different consolidation and drying methods are compared in terms of their final microstructure, porosity, and compressive strength. Consolidation of the wet foam by particle coagulation before drying resulted in porous alumina with a closed-cell structure, a porosity of 86.5%, an average cell size of 35 μm, and a remarkable compressive strength of 16.3 MPa. On the other hand, wet foams consolidated via gelation of the liquid within the foam lamella led to porous structures with interconnected cells in the size range from 100 to 150 μm. The tailored microstructure and high mechanical strength of the macroporous ceramics can be of interest for the manufacture of bio-scaffolds, thermal insulators, impact absorbers, separation membranes, and light weight ceramics.     

Feature selection for k-means clustering stability: theoretical analysis and an algorithm

Stability of a learning algorithm with respect to small input perturbations is an important property, as it implies that the derived models are robust with respect to the presence of noisy features and/or data sample fluctuations. The qualitative nature of the stability property enhardens the development of practical, stability optimizing, data mining algorithms as several issues naturally arise, such as: how “much” stability is enough, or how can stability be effectively associated with intrinsic data properties. In the context of this work we take into account these issues and explore the effect of stability maximization in the continuous (PCA-based) k-means clustering problem. Our analysis is based on both mathematical optimization and statistical arguments that complement each other and allow for the solid interpretation of the algorithm’s stability properties. Interestingly, we derive that stability maximization naturally introduces a tradeoff between cluster separation and variance, leading to the selection of features that have a high cluster separation index that is not artificially inflated by the features variance. The proposed algorithmic setup is based on a Sparse PCA approach, that selects the features that maximize stability in a greedy fashion. In our study, we also analyze several properties of Sparse PCA relevant to stability that promote Sparse PCA as a viable feature selection mechanism for clustering. The practical relevance of the proposed method is demonstrated in the context of cancer research, where we consider the problem of detecting potential tumor biomarkers using microarray gene expression data. The application of our method to a leukemia dataset shows that the tradeoff between cluster separation and variance leads to the selection of features corresponding to important biomarker genes. Some of them have relative low variance and are not detected without the direct optimization of stability in Sparse PCA based k-means. Apart from the qualitative evaluation, we have also verified our approach as a feature selection method for $k$ -means clustering using four cancer research datasets. The quantitative empirical results illustrate the practical utility of our framework as a feature selection mechanism for clustering.     

Role of cognitive and functional performance in the interactions between elderly people with cognitive decline and an avatar on TV

The complexity of new information technologies (IT) may limit the access of elderly people to the information society, exacerbating what is known as “the digital divide,” as they appear to be too challenging for elderly citizens regardless of the integrity of their cognitive status. This study is an attempt to clarify how some cognitive functions (such as attention or verbal memory) may determine the interaction of cognitively impaired elderly people with technology. Twenty participants ranging from mild cognitive impairment to moderate Alzheimer’s disease were assessed by means of a neuropsychological and functional battery and were asked to follow simple commands from an avatar appearing on a TV by means of a remote control, such as asking the participant to confirm their presence or to respond Yes/No to a proposal to see a TV program. The number of correct answers and command repetitions required for the user to respond were registered. The results show that participants with a better cognitive and functional state in specific tests show a significantly better performance in the TV task. The derived conclusion is that neuropsychological assessment may be used as a useful complementary tool for assistive technology developers in the adaptation of IT to the elderly with different cognitive and functional profiles. Further studies with larger samples are required to determine to what extent cognitive functions can actually predict older users’ interaction with technology.     

Water uptake and tensile properties of carboxylated styrene butadiene rubber based water born paints: Models for water uptake prediction

Despite significant advances in water based surface coating technology, the presence of surfactants in emulsion polymer binders leads to loss of performance after prolonged immersion in water, relative to solvent based coatings that are free of surfactant impurities. This study begins with water uptake evaluation of a range of emulsion polymer binders. A carboxylated styrene butadiene rubber latex (c-SBR) performed best in the latter evaluations and was selected for the formulation of an exterior grade paint and construction of a mathematical model to predict water uptake of the dry film. The c-SBR was then compounded with a range of inorganic fillers and water uptake and tensile properties were evaluated. Talc was found to be the best performing filler, and was used in a three factorial central composite design study where the simultaneous effects of talc, titanium dioxide and phenolic stabiliser on water up take were evaluated and fitted to response equations. A quadratic model was found to provide the most accurate prediction of effects associated with interactions between talc and TiO₂. Certain combinations of talc and titanium dioxide were found to be synergistic in reducing the water uptake. This was considered to be associated with a packing effect stemming from the vast difference in particle size between talc and titanium dioxide particles. An optimised formulation was finally prepared to meet one of the final formulation objectives; i.e., minimised water uptake. Preparation of such a formulation showed that the predicted and measured water uptake responses were in excellent agreement. This study illustrates the effectiveness of statistical experimental design methods in predicting the water uptake characteristics of water-based coatings.     

New fluorinated poly(1,3,4-oxadiazole-ether-imide)s

New fluorinated poly(1,3,4-oxadiazole-ether-imide)s have been prepared by solution polycondensation reaction of different aromatic diamines having preformed 1,3,4-oxadiazole ring, such as 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis[p-(4-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2,5-bis[p-(3-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2-(4-dimethylaminophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole and 2-(4-fluorophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole, with an aromatic dianhydride incorporating ether linkages and hexafluoroisopropylidene group, namely 1,1,1,3,3,3-hexafluoro-2,2-bis-[(3,4-dicarboxyphenoxy)phenyl]-propane dianhydride. The polymers were easily soluble in polar organic solvents, such as N-methylpyrrolidinone, N,N-dimethylformamide, and pyridine, as well as in certain low boiling-point organic solvents, such as tetrahydrofuran and chloroform. Very thin coatings deposited onto silicon wafers exhibited smooth, pinhole-free surface in atomic force microscopy. The polymers showed high thermal stability with decomposition temperature being above 410 °C. They exhibited a glass transition in the temperature range of 183-217 °C, with reasonable interval between glass transition and decomposition temperature. Solutions of some polymers in N,N-dimethylformamide exhibited blue fluorescence, having maximum emission wavelength in the range of 411-424 nm.     

Pheromone specificity inEriocrania semipurpurella (Stephens) andE. sangii (Wood) (Lepidoptera: Eriocraniidae) based on chirality of semiochemicals

The fifth abdominal segment of femaleEriocrania semipurpurella (Stephens) andE. sangii (Wood) contains a pair of exocrine glands. Hexane extracts of this segment were prepared from both species and analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). For both species, the EAD active peaks were identified as nonan-2-one, (Z)-6-nonen-2-one, and (Z)-6-nonen-2-ol by means of mass spectrometry and comparison of retention indices with those of synthetic standards. Enantiomeric separation of chiral alcohols from the female extracts was achieved by gas chromatographic analysis on a cyclodextrin column. InE. semipurpurella, a mixture of (2S,6Z)-nonen-2-ol and (2R,6Z)-nonen-2-ol (2: I) was found, whereas inE. sangii (2S,6Z)-nonen-2-ol was the predominant enantiomer and only traces of theR enantiomer were indicated by the antennal response. In field tests, a blend of the three compounds was not attractive to conspecific males. A subtractive assay showed that the alcohol in various enantiomeric mixtures was the only attractive compound, whereas addition of (Z)-6-nonen-2-one to the alcohol completely inhibited the attraction of both species. A trapping experiment including a wide range of ratios between theR andS enantiomers showed that baits containing 95–100% of theS enantiomer were attractive to maleE. sangii, whereas males ofE. semipurpurella were attracted to all tested ratios of the enantiomers. However, the response profiles of maleE. semipurpurella differed between populations from southern Sweden, south Finland, and the Kola Peninsula in Russia. In south Sweden males were maximally attracted to a racemic mixture of the alcohols. At the Kola PeninsulaE. semipurpurella was attracted to baits containing 95–100% of theR enantiomer. In south Finland all tested ratios between 0 and 100%R enantiomer trappedE. semipurpurella, but the trap catches appeared to be bimodally distributed with peaks around 15 and 70%R enantiomer. The trapping results suggest the existence of pheromone races or sibling species among the specimens identified asE. semipurpurella.Dedicated to Prof. H. J. Bestmann on the occasion of his 70th birthday.