Patricia L. Golas

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.

Multisegmented Block Copolymers by 'Click' Coupling of Polymers Prepared by ATRP

Multisegmented block copolymers were prepared by the step-growth click coupling of well-defined block copolymers synthesized by atom transfer radical polymerization (ATRP). α,ω-Diazido-terminated polystyrene-block-poly(ethylene oxide)-block-polystyrene was coupled with propargyl ether in N,N-dimethylformamide in the presence of a CuBr/N,N,N´,N´´,N´´-pentamethyldiethylenetriamine catalyst. The preparation of multisegmented block copolymers was also demonstrated by the click coupling of propargyl ether with another diazido-terminated triblock copolymer, poly(n-butyl acrylate)-block-poly(methyl methacrylate)-block-poly(n-butyl acrylate), and a diazido-terminated pentablock copolymer, polystyrene-block-poly(n-butyl acrylate)-block-poly(methyl methacrylate)-block-poly(n-butyl acrylate)-block-polystyrene. The formation of a product of higher molecular weight and broader molecular weight distribution was verified by triple-detection size exclusion chromatography, which revealed that typically five to seven block copolymers were linked together during the click reaction. Differential scanning calorimetry and dynamic mechanical analysis revealed that the amphiphilic block copolymer behaves as a viscoelastic fluid, while its corresponding multiblock copolymer is an elastic material. The multisegmented block copolymers with partially miscible segments exhibit higher glass transition temperatures than their precursors.

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 polymers 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.

Stable emulsions with thermally responsive microstructure and rheology using poly(ethylene oxide) star polymers as emulsifiers

Poly(ethylene oxide) star polymers (PEO stars) were prepared by atom transfer radical polymerization of 2000 molecular weight PEO methacrylate macromonomer with divinylbenzene as a crosslinking co-monomer. With an average of 460 arms per star, these PEO stars had a 12 nm radius of gyration that is consistent with a dense polymer core surrounded by an extended PEO corona. The PEO stars were extremely efficient emulsifiers, stabilizing cyclohexane-in-water or xylene-in-water emulsions against coalescence for several months at aqueous phase concentrations as low as 0.008 wt% or 0.01 wt%, respectively. Consistent with their emulsifying performance, PEO star adsorption decreased interfacial tension by approximately 22 mN/m and imparted significant dilatational elasticity to the xylene/water interface. PEO stars were thermally responsive, displaying a cloud point upon heating in water that was tuned by addition of kosmotropic electrolytes, and they in turn produced xylene-in-water emulsions that were thermally responsive in terms of the dispersion state of the emulsion droplets and the emulsion rheology. Emulsions prepared at room temperature mainly had non-flocculated droplets. Heating such an emulsion above the cloud point temperature triggered droplet flocculation, but not coalescence, that in turn was associated with increased viscous and elastic moduli of the emulsion measured after cooling back to room temperature. Emulsions that initially were homogenized above the cloud point temperature and then cooled showed neither droplet flocculation nor rheological thickening relative to emulsions that were prepared and held at room temperature. A mechanism based on the bridging behavior of PEO stars adsorbed at the droplet/water interface is postulated to explain this thermal response of the emulsion microstructure.

Poly(Ethylene Oxide) Star Polymer Adsorption at the Silica/Aqueous Interface and Displacement by Linear Poly(Ethylene Oxide)

Multiarm star copolymers with approximately 460 poly(ethylene oxide) (PEO) arms that have a degree of polymerization N = 45 were synthesized via atom transfer radical polymerization (ATRP) of PEO-methacrylate macromonomers in the presence of divinyl benzene cross-linkers. These are an example of molecular or nanoparticulate brushes that are of interest as steric stabilizers or boundary lubrication agents when adsorbed from solution to a solid/aqueous interface. We use ellipsometry to measure adsorption isotherms at the silica/aqueous interface for PEO star polymers and linear PEO chains having molecular weights comparable either to the star polymer or to the individual arms. The compactness of the PEO star polymers (molecular weight 1.2 × 10(6)) yields a saturation surface excess concentration that is approximately 3.5 times greater than that of the high molecular weight (1 × 10(6)) linear PEO. Adsorption of low molecular weight (6000) linear PEO was below the detection limit. Competitive adsorption experiments were conducted with ellipsometry, complemented by independent quartz crystal microbalance with dissipation (QCM-D) measurements. Linear PEO (high molecular weight) displaced preadsorbed PEO star polymers over the course of approximately 1.5 h, to form a mixed adsorbed layer having not only a significantly lower overall polymer surface excess concentration, but also a significantly greater amount of hydrodynamically entrapped water. Challenging a preadsorbed linear PEO (high molecular weight) layer with PEO star polymers produced no measurable change in the overall polymer surface excess concentration, but changes in the QCM-D energy dissipation and resonance frequency suggested that the introduction of PEO star polymers caused a slight swelling of the layer with a correspondingly small increase in entrapped water content.

From Mechanism and Kinetics to Precise ATRP Synthesis

Controlled/living radical polymerizations (CRP) give access to polymers with precisely controlled molecular weight, narrow molecular weight distribution, well-defined architecture and composition. CRP can be applied to a wide range of monomers and are tolerant to impurities and functional groups. Atom transfer radical polymerization (ATRP) is one of the most widely used CRP techniques. The mechanistic and kinetic studies of ATRP are of fundamental importance since they give access to polymers with various functionalities, compositions, and topologies.