ABSTRACT
Optically active polymers are of great interest as materials for dense enantioselective membranes, as well as chiral stationary phases for gas and liquid chromatography. Combining the versatility of norbornene chemistry and the advantages of chiral natural terpenes in one molecule will open up a facile route toward the synthesis of diverse optically active polymers. Herein, we prepared a set of new chiral monomers from cis-5-norbornene-2,3-dicarboxylic anhydride and chiral alcohols of various natures. Alcohols based on cyclic terpenes ((-)-menthol, (-)-borneol and pinanol), as well as commercially available alcohols (S-(-)-2-methylbutanol-1, S-(+)-3-octanol), were used. All the synthesized monomers were successfully involved in ring-opening metathesis polymerization, affording polymers in high yields (up to 96%) and with molecular weights in the range of 1.9 × 105-5.8 × 105 (Mw). The properties of the metathesis polymers obtained were studied by TGA and DSC analysis, WAXD, and circular dichroism spectroscopy. The polymers exhibited high thermal stability and good film-forming properties. Glass transition temperatures for the prepared polymers varied from -30 °C to +139 °C and, therefore, the state of the polymers changed from rubbery to glassy. The prepared polymers represent a new attractive platform of chiral polymeric materials for enantioselective membrane separation and chiral stationary phases for chromatography.
ABSTRACT
The atmospheric pressure solvothermal (APS) synthesis of nanocrystalline SnO2 (average size of coherent scattering regions (CSR)-7.5 ± 0.6 nm) using tin acetylacetonate as a precursor was studied. The resulting nanopowder was used as a functional ink component in microextrusion printing of a tin dioxide thick film on the surface of a Pt/Al2O3/Pt chip. Synchronous thermal analysis shows that the resulting semiproduct is transformed completely into tin dioxide nanopowder at 400 °C within 1 h. The SnO2 powder and the resulting film were shown to have a cassiterite-type structure according to X-ray diffraction analysis, and IR spectroscopy was used to establish the set of functional groups in the material composition. The microstructural features of the tin dioxide powder were analyzed using scanning (SEM) and transmission (TEM) electron microscopy: the average size of the oxide powder particles was 8.2 ± 0.7 nm. Various atomic force microscopy (AFM) techniques were employed to investigate the topography of the oxide film and to build maps of surface capacitance and potential distribution. The temperature dependence of the electrical conductivity of the printed SnO2 film was studied using impedance spectroscopy. The chemosensory properties of the formed material when detecting H2, CO, NH3, C6H6, C3H6O and C2H5OH, including at varying humidity, were also examined. It was demonstrated that the obtained SnO2 film has an increased sensitivity (the sensory response value was 1.4-63.5) and selectivity for detection of 4-100 ppm C2H5OH at an operating temperature of 200 °C.
