Phase Separation Of Nanoparticles Research Articles

Biodegradable zwitterionic nanoparticles with tunable UCST-type phase separation under physiological conditions.

Thermo-responsive polymeric nanoparticles (NPs) are emerging as a powerful tool in nanomedicine for the fabrication of advanced drug delivery systems. In addition to their size and biodegradation rate, phase separation of NPs upon application of a thermal stimulus provides an additional switch to control the rate of release of active components. Among the materials currently developed for biomedical applications, NPs stabilized by zwitterionic polymers are gaining increasing interest due to their high stability and ability to escape the body immune response. Yet, biodegradable zwitterionic NPs with temperature response under physiological conditions are currently not available. Here, we develop a new class of biodegradable zwitterionic NPs that exhibit UCST phase transition in the biological temperature range (T = 30-45 °C) and in physiological solution (i.e. 0.9% w/w NaCl). We design a strategy that relies on the self-assembly of block copolymers produced via reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization. These copolymers comprise a zwitterionic portion exhibiting an upper critical solution temperature (UCST) and a biodegradable hydrophobic block consisting of oligoesters functionalized with a vinyl group. This modular macromolecular architecture allows us to independently control a variety of NP properties by modifying the individual components of the copolymer. In particular, the zwitterionic block of the copolymers controls the UCST-type phase separation behavior, while the number of the oligoester repeating units governs the size of the NPs and the length of the oligoester dictates the degradation rate. After demonstrating the synthesis of highly controlled degradable NPs, we show the potential of this new class of materials in the context of drug delivery by controlling the release of a drug-mimic molecule upon temperature variations in a broad time range from few minutes to 20 hours.

From Flexible to Hard Polyurethane Aerogels: The Effect of Molecular Functionality vs. Molecular Rigidity

ABSTRACTHigh performance all-polymer aerogels are not only interesting for their low thermal conductivity, but also for their mechanical strength and their conversion to porous carbons. The prevalent design rule dictates that crosslinking at the monomer level decreases solubility of the developing polymer and induces phase separation of nanoparticles with high surface to volume ratios. Hence, hyperbranched structures based on trifunctional single aromatic core monomers should have enhanced interparticle connectivity and rigidity compared to those based on either difunctional or multiple aromatic core monomers. That design rule is applied here to hyperbranched polyurethane (PU) aerogels synthesized from tris(4-isocyanatophenyl)methane (TIPM) and 1,1,1-tris(4-hydroxyphenyl)ethane (HPE) in anhydrous acetone using dibutyltin dilaurate (DBTDL) as catalyst. The resulting materials vary from highly flexible to rigid as the monomer concentration increases. FTIR and 13C solid NMR confirm formation of urethane. SEM shows that the flexible variety is macroporous with a beaded worm-like structure, while the rigid variety is mesoporous and nanoparticulate. Lower-density flexible aerogels are highly porous (92%) with surface area of 132 m2 g-1, while the rigid ones have higher surface areas, up to 256 m2 g-1. Polyurethane aerogels from other triols and diols, e.g., phloroglucinol (POL) and resorcinol (RES), respectively, have also been studied and for similar monomer concentrations shrinkage and bulk density increases.

Polymer-mediated growth of fluorescent semiconductor nanoparticles in preformed nanocomposites

In this study, we investigated the size and photoluminescence (PL) evolution of CdTe nanoparticles (NPs) in different polymer media under thermal annealing. A quick growth and maintenance of strong PL were observed. By analyzing the transmission electron microscopy (TEM) images of NPs in polymer media, we discovered that the size evolution of NPs was the combination of Ostwald ripening and dynamic coalescence throughout the growth process. Moreover, the experimental results also revealed that the nature of polymers determined the dynamic coalescence of NPs from three aspects; the mobility of polymer chains, the compatibility of NPs with polymer media, and the interaction between NPs and polymer network. Thus by altering the glass transition temperature (T(g)) of polymers, the molar mass (M(n)) of the polymers, the phase separation of NPs in polymer media, as well as the interaction between NPs and polymers, the growth rate of NPs was controllable.

Forces between functionalized silica nanoparticles in solution

To prevent the flocculation and phase separation of nanoparticles in solution, nanoparticles are often functionalized with short chain surfactants. Here we present fully atomistic molecular dynamics simulations which characterize how these functional coatings affect the interactions between nanoparticles and with the surrounding solvent. For 5-nm-diameter silica nanoparticles coated with poly(ethylene oxide) (PEO) oligomers in water, we determined the hydrodynamic drag on two approaching nanoparticles moving through solvent and on a single nanoparticle as it approaches a planar surface. In most circumstances, macroscale fluid theory accurately predicts the drag on these nanoscale particles. Good agreement is seen with Brenner's analytical solutions for wall separations larger than the soft nanoparticle radius. For two approaching coated nanoparticles, the solvent-mediated (velocity independent) and lubrication (velocity-dependent) forces are purely repulsive and do not exhibit force oscillations that are typical of uncoated rigid spheres.

Publisher’s Note: Fluctuation Mediated Interaction and Phase Separation of Nanoparticles in a Liquid Crystal Solvent [Phys. Rev. Lett.PRLTAO0031-900791, 085704 (2003)

Received 16 September 2003DOI:https://doi.org/10.1103/PhysRevLett.91.139901©2003 American Physical Society

Fluctuation mediated interaction and phase separation of nanoparticles in a liquid crystal solvent.

Water-in-oil microemulsions of nanodroplets in the isotropic phase of a thermotropic liquid crystal exhibit, with decreasing temperature and in anticipation of a demixing transition, enhanced correlation in fluctuations of both molecular orientation and droplet concentration. Mean field modeling of this pretransition behavior, on the basis of a lattice in which the nanodroplets are introduced as holes, shows that the observed interdroplet attractive interaction is produced by the disordering effect of the droplets on the liquid crystal and mediated solely by paranematic fluctuations.