Modelling and Validation of Synthesis of Poly Lactic Acid Using an Alternative Energy Source through a Continuous Reactive Extrusion Process.

PLA is one of the most promising bio-compostable and bio-degradable thermoplastic polymers made from renewable sources. PLA is generally produced by ring opening polymerization (ROP) of lactide using the metallic/bimetallic catalyst (Sn, Zn, and Al) or other organic catalysts in a suitable solvent. In this work, reactive extrusion experiments using stannous octoate Sn(Oct)2 and tri-phenyl phosphine (PPh)3 were considered to perform ROP of lactide. Ultrasound energy source was used for activating and/or boosting the polymerization as an alternative energy (AE) source. Ludovic® software, designed for simulation of the extrusion process, had to be modified in order to simulate the reactive extrusion of lactide and for the application of an AE source in an extruder. A mathematical model for the ROP of lactide reaction was developed to estimate the kinetics of the polymerization process. The isothermal curves generated through this model were then used by Ludovic software to simulate the "reactive" extrusion process of ROP of lactide. Results from the experiments and simulations were compared to validate the simulation methodology. It was observed that the application of an AE source boosts the polymerization of lactide monomers. However, it was also observed that the predicted residence time was shorter than the experimental one. There is potentially a case for reducing the residence time distribution (RTD) in Ludovic® due to the 'liquid' monomer flow in the extruder. Although this change in parameters resulted in validation of the simulation, it was concluded that further research is needed to validate this assumption.

Size effects of self-assembled block copolymer spherical micelles and vesicles on cellular uptake in human colon carcinoma cells.

Block copolymers, poly(oligo ethylene glycol methyl ether methacrylate)-block-poly(styrene), POEGMEMA-b-PS, with various block lengths were prepared via RAFT polymerization and subsequently self-assembled into various aggregates to investigate their uptake ability into human colon carcinoma cell lines, WiDr. By varying the ratio of the hydrophobic to hydrophilic block lengths in the block copolymers various morphologies including spherical micelles, cylindrical micelles (rods), vesicles and large compound micelles could be generated. With increasing length of the hydrophobic block the micelles grew in size until chain stretching caused the transition to rods and then to other aggregates. Micelles of two sizes with a hydrodynamic diameter of 34 and 49 nm, respectively, and two different vesicles (hydrodynamic diameters 99 nm and 150 nm) were further studied towards their ability to be taken up by human colon carcinoma cells. Results indicated that the smaller sized micelles were taken up almost immediately while an increased sized micelle was taken up, however at a slower rate. Though larger vesicle aggregates were taken up at a slower rate, eventually all cells internalized aggregates to a similar amount after a few hours.

Orientation and Dynamics of ZnO Nanorod Liquid Crystals in Electric Fields.

ZnO nanorod polymer hybrids (i.e., ZnO nanorods coated with a block copolymer with a short anchor block (dopamine) and a longer solubilizing block of polystyrene (PS)) form liquid crystalline (LC) phases if they are dispersed at high concentration e.g., in a PS oligomer matrix. Due to the high mobility of the low T(g) -matrix the nanorod polymer hybrids show a switching behavior under an applied AC electric field. Hence, the orientation of the nanorod mesogens can be changed from planar (parallel to the substrate) to homeotropic (perpendicular) in full analogy to the switching of low molecular liquid crystals in an electric field. Dielectric measurements show that such a switching is mainly due to the cooperative LC behavior, because the rods themselves exhibit only a very small effective dipole moment. The process can be investigated by polarizing microscopy. SEM images show the orientations of the individual nanorods, which correspond to the Fredericks transition well known for liquid crystals aligned in an electric field. This was the first time such a transition could be visualized by electron microscopy due to the large nanorod mesogens. The observation is interesting to orient nanorods perpendicular to an electrode and can help to improve optoelectronic devices.