Plasma Polymerization of Acrylic Acid for the Tunable Synthesis of Glassy and Carboxylated Nanoparticles.

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 the polymerization of acrylic acid under the conditions of a glow discharge. In a monomer-deficient regime, the strong fragmentation of 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 carboxyl groups that reaches 16%. All types of NPs exhibit a glass transition above room temperature, which makes them highly stable in an aqueous environment with no dissolution or swelling. The NPs are also found to degrade thermally when heated above 150 °C, with a decrease in the mean NP size but with retention of the chemical composition. Thus, plasma polymerization proves to be a versatile approach for the production of polymer NPs with a tunable size distribution, chemical composition, and physical properties.

Cu nanoparticles constrain segmental dynamics of cross-linked polyethers: a trade-off between non-fouling and antibacterial properties.

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 whereas polyether 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.

Carboxyl-Functionalized Nanoparticles Produced by Pulsed Plasma Polymerization of Acrylic Acid.

Carboxyl-enriched and size-selected polymer nanoparticles (NPs) may prove to be very useful in biomedical applications for linker-free binding of biomolecules and their transport to cells. In this study, we report about the synthesis of such NPs by low-pressure low-temperature pulsed plasma polymerization of acrylic acid. Gas aggregation cluster source was adapted to operate plasma with a constant pulse period of 50 µs and with varying duty cycle. The NPs were produced with the size ranging from 31 ± 5 to 93 ± 14 nm and with retention of the carboxyl groups ranging from 4.0 to 12.0 atom %. Two regimes of the NP formation were identified. In the large duty cycle regime, the NP growth was interfered with by positive ion bombardment which resulted in the ion-driven detachment of the carboxyl species and in the formation of carboxyl-deficient NPs. In the small duty cycle regime, the NP growth was accompanied by the radical-driven chain propagation with the attachment of intact monomer molecules. Improved efficacy of the monomer retention resulted in increased concentration of the carboxyl groups.