The synthetic approach to the new class of mesomorphous nanocomposite polymer systems was developed. It is based on the in situ reduction of silver ions in the liquid crystalline (LC) polymer matrix leading to the formation of nanoparticles with typical sizes in the range of 5-30 nm. The influence of silver nanoparticles on the phase state of the LC composites, i.e., type and temperature interval of the mesophase, was studied. Regardless of chemical structure of the LC polymer matrix, an increase in the metal concentration is accompanied by a decrease of clearing temperature due to adsorption of macromolecules on the nanoparticle's surface. In the case of an LC copolymer with cyanobiphenyl side mesogenic fragments, the complete disruption of mesophase is observed below 2 wt% content of silver. This phenomenon is, most likely, a result of chemosorption of terminal cyano groups on the nanoparticles with the formation of sigma complexes that disturb packing of the mesogenic units.
The interaction of DNA with amino-functionalized polystyrene particles has been studied by using a dynamic light scattering (DLS) technique. In 10 mM NaBr solution the particles have a hydrodynamic radius of 76 nm and the DNA macromolecule investigated (double stranded) has a hydrodynamic radius of 107 nm. At very low DNA concentrations, DNA adopts a flat conformation on the particle surface. If the DNA concentration is increased above 0.1 microg/mL, the thickness of the DNA layer increases, suggesting the presence of large loops and tails. Although the particles contain primary amino groups, they have a negative net charge under the conditions used in this work. Thus, the driving force for DNA adsorption is not of electrostatic origin but rather due to a hydrophobic effect. Addition of cationic surfactant to the DNA-precoated amino-functionalized particles induces changes in the adsorbed layer conformation, in agreement with the coadsorption of cationic surfactant.
New polymer nematic nanocomposites are prepared containing 1.43-4.64 wt % of silver nanoparticles whose mean dimensions are 2-4 nm. According to 2 H NMR spectroscopic measurements, on increasing the content of metallic nanoparticles, the orientational order parameter S zz of the nematic phase shown by the nanocomposites increases.
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