Microbial bioavailability of covalently bound polymer coatings on model engineered nanomaterials.

By controlling nanoparticle flocculation and deposition, polymer coatings strongly affect nanoparticle fate, transport, and subsequent biological impact in the environment. Biodegradation is a potential route to coating breakdown, but it is unknown whether surface-bound polymers are bioavailable. Here we demonstrate, for the first time, that polymer coatings covalently bound to nanomaterials are bioavailable. Model poly(ethylene oxide) (PEO) brush-coated nanoparticles (densely cross-linked bottle brush copolymers) with hydrophobic divinyl benzene cross-linked cores and hydrophilic PEO brush shells, having ~ 30 nm hydrodynamic radii, were synthesized to obtain a nanomaterial in which biodegradation was the only available coating breakdown mechanism. PEO-degrading enrichment cultures were supplied with either PEO homopolymer or PEO brush nanoparticles as the sole carbon source, and protein and CO2 production were monitored as a measure of biological conversion. Protein production after 90 h corresponded to 14% and 8% of the total carbon available in the PEO homopolymer and PEO brush nanoparticle cultures, respectively, and CO2 production corresponded to 37% and 3.8% of the carbon added to the respective system. These results indicate that the PEO in the brush is bioavailable. Brush biodegradation resulted in particle aggregation, pointing to the need to understand biologically mediated transformations of nanoparticle coatings in order to understand the fate and transport of nanoparticles in the environment.

Comparative study of polymeric stabilizers for magnetite nanoparticles using ATRP.

A series of polyelectrolytes with controlled molecular weight, a narrow chain-length distribution, and systematic structural differences were synthesized using atom-transfer radical polymerization and investigated as stabilizers for magnetite nanoparticles in aqueous suspensions. Structural differences include the degree of polymerization, the chain architecture, and the identity of the charged functional unit. The synthesized polymers are sulfonated poly(2-hydroxyethyl methacrylate), a block copolymer of the former with poly(n-butyl methacrylate), poly(sodium styrene sulfonate), poly(sodium acrylate), and poly(sodium vinylphosphonate). The colloidal stability is assessed by measuring the fraction of particles, based on turbidity, that sediment after a period of time at increasing ionic strength. Sedimentation results are complimented by dynamic light scattering determinations of the hydrodynamic diameter of the particles that remain suspended. When adsorption and sedimentation are conducted at high pH, poly(sodium acrylate) and poly(sodium vinylphosphonate) yield the most stable suspensions because of their strong coordinative interactions with the iron oxide surface. At low pH, the polymers that retain pendant negative charges (each of the sulfonated polymers) yield high stable fractions at all ionic strengths investigated up to 100 mM (NaCl), whereas polyelectrolytes that become protonated with decreasing pH, poly(sodium acrylate) and poly(sodium vinylphosphonate), lose their stabilizing capacity even at low ionic strengths. The chain-length distribution profoundly alters a polymer's stabilization tendencies. Two poly(sodium acrylate) samples with the same number-average molecular weight but widely different chain-length distributions proved to have opposite tendencies, with the polydisperse sample being a good stabilizer and the low polydispersity one being a strong flocculant. This investigation provides guidelines for the design of polymeric stabilizers for magnetite nanoparticles according to the pH and ionic strength of the intended application.

Marrying click chemistry with polymerization: expanding the scope of polymeric materials.

Click chemistry constitutes a class of reactions broadly characterized by efficiency, selectivity, and tolerance to a variety of solvents and functional groups. By far the most widely utilized of these efficient transformation reactions is the Cu(I)-catalyzed azide-alkyne cycloaddition. This reaction has been creatively employed to facilitate the preparation of complex macromolecules, such as multiblock copolymers, shell or core cross-linked micelles, and dendrimers. This critical review highlights the application of click chemistry, in particular the Cu(I)-catalyzed azide-alkyne cycloaddition, to the synthesis of a wide variety of new materials with possible uses as drug delivery agents, tissue engineering scaffolds, and dispersible nanomaterials (83 references).

Effect of adsorbed polyelectrolytes on nanoscale zero valent iron particle attachment to soil surface models.

Polyelectrolyte coatings significantly increase the mobility of nanoscale zerovalent iron (NZVI) in saturated porous media. The effect can be attributed to improved colloidal stability of NZVI suspensions, decreased adhesion to soil surfaces, or a combination of the two effects. This research explicitly examines how coatings control NZVI adhesion to model soil surfaces. NZVI was coated with three different polyeleotrolyte block copolymers based on poly(methacrylic acid), poly(methyl methacrylate or butyl methacrylate), and poly(styrenesulfonate) or with a poly(styrenesulfonate) homopolymer. SiO2 and a humic acid film served as model soil surfaces. The polyelectrolytes increased the magnitude of the electrophoretic mobility of NZVI over a broad pH range relative to unmodified NZVI and shifted the isoelectric point outside the typical groundwater pH range. Quartz crystal microgravimetry measurements indicated extensive adhesion of unmodified NZVI to SiO2. Polyelectrolyte coatings decreased adhesion by approximately 3 orders of magnitude. Adding 50 mM NaCL to screen electrostatic repulsions did not significantly increase adhesion of modified NZVI. Coated NZVI did not adhere to humic acid films for either 1 mM NaHCO3 or 1 mM NaHCO3 + 50 mM NaCl. The lack of adhesion even in a high ionic strength medium was attributed to electrosteric repulsion, as opposed to electrostatic double layer repulsion, between the polyelectrolyte-coated NZVI and the negatively charged surfaces. The lack of significant adhesion on either model surface was observed for all polymer architectures investigated.