Nanoanesthesia: a novel, intravenous approach to ankle block in the rat by magnet-directed concentration of ropivacaine-associated nanoparticles.

BACKGROUND: As an alternative to current methods of local nerve block, we studied the feasibility of producing ankle block in the rat with IV injection of magnetic nanoparticles (MNPs) associated with ropivacaine and application of a magnet at the ankle. METHODS: The anesthetic effect of magnet-directed ropivacaine-associated MNPs (MNP/Ropiv) was tested in the rat using paw withdrawal latencies from thermal stimuli applied to the hindpaw. The MNP/Ropiv complexes consisted of 0.7% w/v ropivacaine and 0.8% w/v MNPs containing 12% w/w magnetite (F3O4). The effect of IV injection of MNP/Ropiv with 15, 30, and 60-minute magnet application to the right ankle was compared with the effect without magnet application on the left hindpaw, to conventional ankle block with 0.1% or 0.2% ropivacaine, and to IV injection of MNPs alone with 30-minute magnet application to the right ankle. In addition, the pharmacokinetics of the MNP/Ropiv complexes were determined. RESULTS: IV injection of MNP/Ropiv with magnet application at the ankle significantly increased paw withdrawal latencies from thermal stimuli compared with pretreatment baselines in the same paw (P < 0.0001) and compared with the contralateral paw without magnet application (P < 0.0001). IV injection of MNPs alone had no significant effect on paw withdrawal latency. Absolute ropivacaine concentrations in ankle tissue, and ankle tissue-to-plasma concentration ratios were higher in the MNP/Ropiv group with 30-minute magnet application compared with MNP/Ropiv group without magnet application (mean ± SEM, 150 ± 10 ng/g vs 105 ± 15 ng/g, respectively, and 6.1 ± 0.8 vs 4.2 ± 0.7, respectively). CONCLUSIONS: The current study establishes proof of principle that it is possible to produce ankle block in the rat by IV injection of MNP/Ropiv complexes and magnet application at the ankle. The results indicate that further study of this approach is warranted.

Recyclable antibacterial magnetic nanoparticles grafted with quaternized poly(2-(dimethylamino)ethyl methacrylate) brushes.

Highly efficient recyclable antibacterial magnetite nanoparticles consisting of a magnetic Fe(3)O(4) core with an antibacterial poly(quaternary ammonium) (PQA) coating were prepared in an efficient four-step process. The synthetic pathway included: (1) preparation of Fe(3)O(4) nanoparticles via coprecipitation of Fe(2+)/Fe(3+) in the presence of an alkaline solution; (2) attachment of an ATRP initiating functionality to the surface of the nanoparticles; (3) surface-initiated atom transfer radical polymerization (ATRP) of 2-(dimethylamino)ethyl methacrylate (DMAEMA); and (4) transformation of PDMAEMA brushes to PQA via quaternization with ethyl bromide. The success of the surface functionalization was confirmed by FT-IR, thermal gravimetric analysis (TGA), elemental analysis, and transmission electron microscopy (TEM). The PQA-modified magnetite nanoparticles were dispersed in water and exhibited a response to an external magnetic field, making the nanoparticles easy to remove from water after antibacterial tests. The PQA-modified magnetite nanoparticles retained 100% biocidal efficiency against E. coli (10(5) to 10(6)E. coli/mg nanoparticles) during eight exposure/collect/recycle procedures without washing with any solvents or water.

Silica-polymethacrylate hybrid particles synthesized using high-pressure atom transfer radical polymerization.

Hybrid nanoparticles with a silica core and grafted poly(methyl methacrylate) (PMMA) or poly(n-butyl methacrylate) (PBMA) chains were prepared via activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) at room temperature under high pressure. Due to enhanced propagation rate constant and reduced termination rate constant for polymerizations conducted under high pressure, the rate of polymerization was increased, while preserving good control over polymerization when compared to ATRP under ambient pressure. Molecular weights of greater than 1 million were obtained. The PMMA and PBMA brushes exhibited "semi-diluted" or "diluted" brush architecture with the highest grafting densities ≈0.3 chain·nm(-2).

Flexible particle array structures by controlling polymer graft architecture.

Surface-initiated atom-transfer radical polymerization is used to synthesize particle brushes with controlled fraction of extended and relaxed conformations of surface-grafted chains. In the semidilute brush limit, the grafting of polymeric ligands is shown to facilitate the formation of ordered yet plastic-compliant particle array structures in which chain entanglements give rise to fracture through a polymer-like crazing process that dramatically increases the toughness and flexibility of the particle assembly.

Pickering emulsions stabilized by nanoparticles with thermally responsive grafted polymer brushes.

A study is presented of emulsification by silica nanoparticles with poly(2-(dimethylamino)ethyl methacrylate) brushes grafted from their surfaces (SiO(2)-PDMAEMA) by atom-transfer radical polymerization (ATRP). The grafted nanoparticles were used to stabilize xylene-in-water and cyclohexane-in-water Pickering emulsions. PDMAEMA is a water-soluble weak polyelectrolyte with a pH-dependent lower critical solution temperature (LCST). Accordingly, SiO(2)-PDMAEMA nanoparticles were thermally responsive, as shown by the fact that they displayed a critical flocculation temperature (CFT) when heated. ATRP provides a high degree of control over the brush grafting density and degree of polymerization, two of the principal variables examined in this study. The effects of the solvent quality of the "oil" for the PDMAEMA brush were studied in addition to the effects of aqueous pH, ionic strength, and temperature relative to the CFT. The preferred emulsion type was oil in water in all cases. The lowest grafting density particles (0.077 chains/nm(2)) proved to be the most efficient and robust emulsifiers, producing stable emulsions using as little as 0.05 wt % particles in the aqueous phase and successfully emulsifying over a broader range of solution conditions than for the higher grafting density particles (0.36 and 1.27 chain/nm(2)). Both good (xylene) and poor (cyclohexane) solvents could be emulsified, but the poor solvent could be emulsified over a broader range of conditions than the good solvent. Emulsions have been stable for over 13 months, and some have dispersed as much as 83 vol % oil in the emulsion phase. Thermally responsive emulsions were created with the SiO(2)-PDMAEMA particles such that stable emulsions prepared at low temperature were rapidly broken by increasing the temperature above the CFT.

Impact of polymer graft characteristics and evaporation rate on the formation of 2-D nanoparticle assemblies.

The effect of polymer functionalization on the two-dimensional (2-D) assembly of uniform as well as highly asymmetric binary colloidal mixtures with both neutral and incompatible polymer grafts is presented. In ordered assemblies of uniform particle brush systems, the observed size-segregation is analogous to that of hard sphere colloidal systems, suggesting that lateral capillary interactions are responsible for the crystal nucleation in the early stages of assembly formation. Structure formation in binary blends of asymmetric particle brush systems is found to be strongly influenced by three major energetic contributions, that is, the interfacial energies associated with the particle brush/air boundaries, the interfacial energies between the distinct brush components, as well as the elastic energy associated with the stretching of the polymer-brush to fill the interstitial regions within locally ordered particle arrays. Our results demonstrate the relevance of capillary interactions in soft particle brush systems but also highlight distinctive differences in the order formation as compared to hard sphere colloidal systems. In particular, the compliant response of grafted polymer chains is shown to promote phase separation in binary blends of incompatible and asymmetric colloidal systems.

Superhydrophilic surfaces via polymer-SiO2 nanocomposites.

A novel procedure for the preparation of superhydrophilic surfaces is described. The method employs fabricating the surface from a mixture of silica nanoparticles (NPs) and polymers containing reactive trimethoxysilyl (TMOS) groups. Suitable polymers include quaternized poly(2-(dimethylamino)ethyl methacrylate) (PQDMAEMA) and poly(3-(trimethoxysilyl)propyl methacrylate) (PTMOSPMA). Condensation of the TMOS groups in a deposited film occurs under mild conditions and results in formation of a cross-linked polymer-SiO(2) nanocomposite coating covalently anchored onto a glass substrate. When silica nanoparticles, containing micrometer-sized agglomerates, are introduced into the film, a hierarchical micro/nanostructure within the coating is built up. Superhydrophilic behavior is achieved with a high weight ratio of fumed silica NPs or polymer/fumed silica NP bilayer coatings. The superhydrophilic surfaces have high stability and antifogging behavior and display easy cleaning characteristics. Furthermore, the superhydrophilic nanocomposite coatings containing PQDMAEMA exhibit antimicrobial properties against E. coli due to the presence of quaternary ammonium groups.

One-pot synthesis of robust core/shell gold nanoparticles.

A one-pot synthesis of thermally stable core/shell gold nanoparticles (Au-NPs) was developed via surface-initiated atom transfer radical polymerization (ATRP) of n-butyl acrylate (BA) and a dimethacrylate-based cross-linker. The higher reactivity of the cross-linker enabled the formation of a thin cross-linked polymer shell around the surface of the Au-NP before the growth of linear polymer chains from the shell. The cross-linked polymer shell served as a robust protective layer, prevented the dissociation of linear polymer brushes from the surfaces of Au-NPs, and provided the Au-NPs excellent thermal stability at elevated temperature (e.g., 110 degrees C for 24 h). This synthetic method could be easily expanded for preparation of other types of inorganic/polymer nanocomposites with significantly improved stability.

Anisotropic elasticity of quasi-one-component polymer nanocomposites.

The in-plane and out-of-plane elastic properties of thin films of "quasi-one-component" particle-brush-based nanocomposites are compared to those of "classical" binary particle-polymer nanocomposite systems with near identical overall composition using Brillouin light scattering. Whereas phonon propagation is found to be independent of the propagation direction for the binary particle/polymer blend systems, a pronounced splitting of the phonon propagation velocity along the in-plane and out-of-plane film direction is observed for particle-brush systems. The anisotropic elastic properties of quasi-one-component particle-brush systems are interpreted as a consequence of substrate-induced order formation into layer-type structures and the associated breaking of the symmetry of the film. The results highlight new opportunities to engineer quasi-one-component nanocomposites with advanced control of structural and physical property characteristics based on the assembly of particle-brush materials.

Dangling chain elastomers as repeatable fibrillar adhesives.

This work reports on repeatable adhesive materials prepared by controlled grafting of dangling hetero chains from polymer elastomers. The dangling chain elastomer system was prepared by grafting poly(n-butyl acrylate) (PBA) chains from prefunctionalized polydimethylsiloxane (PDMS) elastomer networks using atom transfer radical polymerization. To study the effects of chain growth and network strain as they relate to network adhesion mechanics, various lengths of PBA chains with degree of polymerizations (DP) of 65, 281, 508, and 1200 were incorporated into the PDMS matrix. PBA chains with a DP value of 281 grafted from a flat PDMS substrate showed the highest (approximately 3.5-fold) enhancement of nano- and macroscale adhesion relative to a flat raw (ungrafted and not prefunctionalized) PDMS substrate. Moreover, to study the effect of PBA dangling chains on adhesion in fibrillar elastomer structures inspired by gecko foot hairs, a dip-transfer fabrication method was used to graft PBA chains with a DP value of 296 from the tip endings of mushroom-shaped PDMS micropillars. A PBA chain covered micropillar array showed macroscale adhesion enhancement up to approximately 7 times relative to the flat ungrafted prefunctionalized PDMS control substrate, showing additional nonoptimized approximately 2-fold adhesion enhancement due to fibrillar structuring and mushroom-shaped tip ending. These dangling hetero chains on elastomer micro-/nanofibrillar structures may provide a novel fabrication platform for multilength scale, repeatable, and high-strength fibrillar adhesives inspired by gecko foot hairs.

Grafting from surfaces for "everyone": ARGET ATRP in the presence of air.

Atom-transfer radical polymerization (ATRP) is one of the controlled/living radical polymerizations yielding well-defined (co)polymers, nanocomposites, molecular hybrids, and bioconjugates. ATRP, as in any radical process, has to be carried out in rigorously deoxygenated systems to prevent trapping of propagating radicals by oxygen. Herein, we report that ATRP can be performed in the presence of limited amount of air and with a very small (typically ppm) amount of copper catalyst together with an appropriate reducing agent. This technique has been successfully applied to the preparation of densely grafted polymer brushes, poly(n-butyl acrylate) homopolymer, and poly(n-butyl acrylate)-block-polystyrene copolymer from silicon wafers (0.4 chains/nm2). This simple new method of grafting well-defined polymers does not require any special equipment and can be carried out in vials or jars without deoxygenation. The grafting for "everyone" technique is especially useful for wafers and other large objects and may be also applied for molecular hybrids and bioconjugates.