TY - JOUR A1 - Pleskunov, P. A1 - Nikitin, D. A1 - Tafiichuk, R. A1 - Shlemin, A. A1 - Hanus, J. A1 - Kousal, J. A1 - Krtous, Z. A1 - Khalakhan, I. A1 - Kus, P. A1 - Nasu, T. A1 - Nagahama, T. A1 - Funaki, C. A1 - Sato, H. A1 - Gawek, Marcel A1 - Schönhals, Andreas A1 - Choukourov, A. T1 - Plasma polymerization of acrylic acid for the tunable synthesis of glassy abd carboxylated nanoparticle JF - The Journal of Physical Chemistry B N2 - Polymer nanoparticles (NPs) can be highly attractive in numerous applications including biomedicine where the use of inorganic matter may be detrimental for living tissues. In conventional wet chemistry, polymerization and functionalization of NPs with specific chemical groups involves complex and often numerous reactions. Here, we report on a solvent-free, single-step, low temperature plasma-based synthesis of carboxylated NPs produced by polymerization of acrylic acid under the conditions of a glow discharge. In a monomer-deficient regime, strong fragmentation of the monomer molecules by electron impact results in the formation of 15 nm-sized NPs with <1% retention of the carboxyl groups. In an energy-deficient regime, larger 90 nm-sized NPs are formed with better retention of the carboxyls that reaches 16 %. All types of the NPs exhibit the glass transition above the room temperature which makes them highly stable under aqueous environment with no dissolution or swelling. They are also found to degrade thermally when heated above 150 °C with a decrease of the mean NP size, yet with the retention of the chemical composition. Thus, plasma polymerization proves to be a versatile approach for the production of polymer NPs with tuneable size distribution, chemical composition and physical properties. KW - Nanoparticles PY - 2020 DO - https://doi.org/10.1021/acs.jpcb.9b08960 VL - 124 SP - 668 EP - 678 PB - ACS AN - OPUS4-50351 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nikitin, D. A1 - Madkour, Sherif A1 - Pleskunov, P A1 - Tafiichuk, R A1 - Shelemin, A A1 - Hanus, J A1 - Gordeev, I A1 - Sysolyatina, E A1 - Ermolaeva, S A1 - Titov, V A1 - Schönhals, Andreas A1 - Choukourov, A T1 - Cu nanoparticles constrain segmental dynamics of crosslinked polyethers: a trade -off between non-fouling and antibacterial properties JF - Soft Matter N2 - Copper has a strong bactericidal effect against multi-drug resistant pathogens and polyethers are known for their resistance to biofilm formation. Herein, we combined Cu nanoparticles (NPs) and a polyether Plasma polymer in the form of nanocomposite thin films and studied whether both effects can be coupled. Cu NPs were produced by magnetron sputtering via the aggregation in a cool buffer gas whereasolyether layers were synthesized by Plasma-Assisted Vapor Phase Deposition with poly(ethylene oxide) (PEO) used as a precursor. In situ specific heat spectroscopy and XPS analysis revealed the formation of a modified polymer layer around the NPs which propagates on the scale of a few nanometers from the Cu NP/polymer interface and then transforms into a bulk polymer phase. The chemical composition of the modified layer is found to be ether-deficient due to the catalytic influence of copper whereas the bulk polymer Phase exhibits the chemical composition close to the original PEO. Two cooperative glass transition phenomena are revealed that belong to the modified polymer layer and the bulk phase. The former is characterized by constrained mobility of polymer segments which manifests itself via a 30 K increase of dynamic glass transition temperature. Furthermore, the modified layer is characterized by the heterogeneous structure which results in higher fragility of this layer as compared to the bulk phase. The Cu NPs/polyether thin films exhibit reduced Protein adsorption; however, the constrained segmental dynamics leads to the Deterioration of the non-fouling properties for ultra-thin polyether coatings. The films are found to have a bactericidal effect against multi-drug resistant Gram-positive Methicillin-Resistant Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa. KW - Nanocomposites KW - Specific heat spectroscopy PY - 2019 DO - https://doi.org/10.1039/c8sm02413h VL - 15 IS - 13 SP - 2884 EP - 2896 PB - RSC AN - OPUS4-47765 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -