A short synthesis of protected 3-deoxy-d-arabino-2-heptulosonates (DAH) from shikimic acid based on silyl group migration

The reaction of (2S,3S,4R)-2,3,4,7-tetrahydroxy-6-oxoheptanals with lower alcohols produced protected 3-deoxy-d-arabino-2-heptulosonates. The key transformation is based on an 1,4-O–O silyl group migration, followed by 6-exo-trig cyclisation to give the final pyranose.     

Conformally flat,minimal, Lagrangian submanifolds in complex space forms

We investigate n-dimensional (n ⩾ 4), conformally flat, minimal, Lagrangian submanifolds of the n-dimensional complex space form in terms of the multiplicities of the eigenvalues of the Schouten tensor and classify those that admit at most one eigenvalue of multiplicity one. In the case where the ambient space is ℂⁿ, the quasi umbilical case was studied in Blair (2007). However, the classification there is not complete and several examples are missing. Here, we complete (and extend) the classification and we also deal with the case where the ambient complex space form has non-vanishing holomorphic sectional curvature.

     

Thermal and structural stability of composite systems based on polyaniline deposited on porous polyethylene films

Conducting composite systems containing polyaniline layers produced on the surface and inside the pores of polyethylene support have been prepared. Microporous polyethylene films were obtained by melt extrusion with subsequent annealing, uniaxial extension, and thermal fixation. Polyaniline layers were formed by in-situ polymerization of aniline onto polyethylene porous support placed into the aqueous reaction mixture. Structural and chemical transformations upon heating of these systems in air in free state and in vacuum under load have been investigated by thermo-mechanical tests, IR spectrometry, and electron microscopy. Changes in mechanical properties of composites after heating have been analyzed. Composite systems have been found to demonstrate a considerably lower shrinkage upon heating than microporous polyethylene substrates. It has been discovered that the composites preserve mechanical integrity on heating up to temperatures much higher than the polyethylene melting point. It is concluded that thermo-mechanical behaviour of the composites is determined by the space-continuous phase of polyaniline on the surface and in the bulk of polyethylene support.     

A methyltitanocene complex of schisandrol A with high efficacy against multi‐drug resistant cervix and breast carcinoma cells

The objective of this work was to combine the ABC‐transporter inhibition characteristic of esters of the Schisandra sphenantera metabolite schisandrol A with the growth inhibitory and anti‐migratory effects typical of titanium complexes. To this end dimethyltitanocene, (h⁵‐C₅H₅)₂Ti(CH₃)₂, was reacted with the vicinal diol schisandrol A to afford the schisandroxy(methyl)titanocene ( 1 ) as a stable water‐soluble solid. In MTT assays against seven tumor cell lines it proved distinctly more cytotoxic than schisandrol A or dimethyltitanocene or combinations of these. It reached single‐digit micromolar IC₅₀(72 h) values against cells of leukemia HL‐60, melanoma 518A2 and also resistant cervix carcinoma KB‐V1/vbl and resistant breast carcinoma MCF‐7/topo. Non‐malignant fibroblasts were virtually insensitive to it [IC₅₀ (72 h) > 50 µM ]. In addition, the new complex inhibited the p‐gp drug transporters of KB‐V1/vbl cells and prevented a regrowth and closure of scratch wounds in cancer cell cultures (‘wound‐healing’ assay) when applied in concentrations < 1 µM , which is an indication of a potential anti‐migratory and anti‐invasive activity in solid tumors. Copyright © 2010 John Wiley & Sons, Ltd.     

The stability of polyaniline in strongly alkaline or acidic aqueous media

Polyaniline (PANI) base has been suspended in 9 M potassium hydroxide at 20 °C or 90 °C for various time intervals extending to 4 months. The fraction of acetone-soluble material increased from 1.2 wt.% to 4.5 wt.% after exposure to an alkaline medium for 60 days at 20 °C. Gel-permeation chromatography indicates that the aggregation of PANI is reduced, while the chain degradation itself is negligible. FTIR spectroscopy confirms this trend and the absence of hydrolytic changes in the PANI structure. Polyaniline retains the ability to be reprotonated with a 1 M sulfuric acid to a conducting form. No marked changes in the molecular structure have been found, even after suspension of PANI in 9 M KOH at 90 °C for 60 days.Similar immersion of PANI salt in 5 M sulfuric acid at 20 °C was responsible for changes in the protonation, and the mass increased by 11 wt.%. This was explained by the exchange of the original sulfate or chloride counter-ions for hydrogen sulfate anions or by the protonation of secondary amine sites in PANI in addition to imine ones. The changes in the molecular structure are discussed on the basis of FTIR spectra. The conductivity decreased from 1.2 S cm⁻¹ to ∼10⁻³ S cm⁻¹ but no time-dependence of conductivity was observed. There was no fraction of PANI soluble in acetone. PANI in the protonated state is thus stable also in the strongly acidic medium.The study is supplemented by the assessment of the thermal stability of PANI base, which is of importance for the processing of PANI. Loss of moisture has been observed after exposure to 250 °C for 10 h in both nitrogen atmosphere and in air. Good stability was found at 350 °C only in the nitrogen atmosphere, while a marked mass loss in weight was registered in air.     

Influence of selected biowaste materials pre-treatment on their anaerobic digestion

The topic of this study is the pre-treatment of substrates for anaerobic digestion. Two different substrates of algae Scenedesmus subspicatus (SAG 86.81), Chlorella kessleri (LARG/1) and foliage of Prunus serrulata were subjected to anaerobic digestion. A mixture of commercially available cellulolytic enzymes (Analytical science s.r.o., Modra, Slovakia) was used for anaerobic treatment of algae while the foliage of Prunus serrulata was pre-treated by lignolytic fungi. The highest production of methane per mass of volatile solids was reached with untreated Chlorella kessleri at (0.59 ± 0.04) L g⁻¹. The addition of cellulolytic enzymes did not increase the production of methane from the algal substrate; however, a faster substrate degradation and thus also higher speed of methane production at the beginning of cultivation was achieved. After foliage pre-treatment by fungal isolate Pleurotus pulmonarius, isolated from natural habitats, the methane production increased five times. In this way we were able to speed up the processes of biological degradation of ligno-cellulose materials and thereby to increase the production of methane. Our results show the possibility of using algae as a suitable substrate for biogas production. On the other hand, also aerobic pre-treatment of foliage (Pleurotus pulmonarius) presents a successful way for speeding up the degradation of ligno-cellulose waste leading to increased methane yields.     

The effects on soil/water/plant/animal systems by platinum group elements

Emissions of toxic substances such as oxides of carbon, nitrogen, sulphur, and, in addition, aromatic hydrocarbons, aldehydes and heavy metals are the most serious problem of road traffic affecting landscape. Platinum group elements (PGE), which are the main component of the catalyst, are one of the main sources of heavy metals in the environment. Here, we review the way by which emissions and forms of the emitted PGE end up in the environment especially to the soil-water-plant-animal system. The major points discussed are the following: 1) the main sources of PGE emission are automobile exhaust catalysts; 2) hospitals, where platinum is widely used to treat malignant neoplasm, and urban waste water belonging to other important sources of PGE in the environment; 3) soil is one of the most important components of the environment that may be contaminated with platinum metals; 4) phytotoxicity of PGE depends on the following conditions: the concentration of metals in the soil, time of exposure, the chemical form of metal, the chemical composition of exposed soil and plant species; 5) animals are also endangered by the increasing concentration of PGE in the environment. Moreover, we pay our attention to thiol-based mechanisms of how an organism protects itself against platinum group elements.