Aluminum aminoterephthalate MOF particulate materials (NH(2)-MIL-101(Al) and NH(2)-MIL-53(Al)), studied here as components of self-detoxifying surfaces, retained their reactivity following their covalent attachment to protective surfaces utilizing a newly developed strategy in which the MOF particles were deposited on a reactive adhesive composed of polyisobutylene/toluene diisocyanate (PIB/TDI) blends. Following MOF attachment and curing, the MOF primary amino groups were functionalized with highly nucleophilic 4-methylaminopyridine (4-MAP) by disuccinimidyl suberate-activated conjugation. The resulting MOF-4-MAP modified PIB/TDI elastomeric films were mechanically flexible and capable of degrading diisopropyl fluorophosphate (DFP), a chemical threat simulant.

Bactericidal paramagnetic particles were obtained either through the attachment of a conjugate of poly(ethyleneimine) (PEI) and poly(hexamethylene biguanide) (PHMBG) to the surface of magnetite (Fe(3)O(4)) particles, or via the sol-gel encapsulation of magnetite particles with a functional silane (3-glycidoxypropyl trimethoxysilane) and subsequent binding of the polysiloxane shell by the amine/imine groups of PHMBG. The encapsulated core-shell particles possess a high saturation magnetization, which is preserved for more than 10 months while in contact with air in aqueous suspensions. The minimum inhibitory concentration (MIC) of the encapsulated particles for eight types of bacteria was size-dependent, with polydisperse submillimeter particles possessing a several-fold higher MIC than analogous particles sized below 250 nm. The encapsulated particles are biocompatible and nontoxic to mammalian cells such as mouse fibroblasts. The particles efficiently bind both glycopeptide components mimicking the gram-positive bacteria membranes and whole bacteria, and possess broad-range bactericidal activity. The cell-particle complexes can be captured, manipulated, and removed by means of a magnet.

Magnetite and metallic cobalt-based nanoparticles with sizes ranging from 10 to 300 nm and surface-functionalized with poly(hexamethylene biguanide) (PHMBG) are introduced as capable lipopolysaccharide (LPS)-sequestering agents. The nanoparticles efficiently bind to whole E. coli cells and can be used to separate the cells effectively from suspension using a magnet. A fluorescence dye displacement assay shows strong affinities of the nanoparticles for lipid A, the glycolipid component of LPS responsible for septic shock. The particle-lipid A affinity is of the same order of magnitude or higher than that of polymyxin B. The affinity of smaller (< 50 nm) magnetite particles modified with PHMBG to lipid A is several-fold higher than that of their larger counterparts (> 100 nm) due to their higher surface area to volume ratio. The nanoparticles possess high saturation capacity for double-stranded lambdaDNA from E. coli, with which particle-polyelectrolyte complexes are formed. The PHMBG-modified nanoparticles are potent bactericides, inhibiting E. coli viability and growth at concentrations at < or = 10 microg/mL.

We discuss the integration of membrane emulsification and pervaporation processes for the continuous production of functional materials, such as silica-encapsulated magnetite nanoparticle clusters and asymmetric Janus nanoparticles, by the emulsion droplet solvent evaporation method, which has traditionally been performed in small-scale batch systems. An organic solvent containing primary magnetite nanoparticles (∼10 nm) coated with oleic acid was dispersed in a continuous aqueous phase by membrane emulsification, which enabled the consistent production of nanoparticle-laden solvent droplets of well-controlled size with narrow size distributions. The solvent was removed from the emulsion by pervaporation. Prior to complete solvent removal, the nanoparticle packing density within the clusters was a function of the residence time in the pervaporation unit. The final clusters formed, ∼100-300 nm in size, exhibited the same superparamagnetic behavior as the primary nanoparticles, and were stable in aqueous media with a zeta potential of -70 mV at neutral pH. A facile method was used to coat the nanoclusters with a silica shell, providing sites for surface functionalization with a range of organic ligands. The nanoparticles and clusters were analyzed by a variety of techniques, including TGA, DLS, TEM, EDS, and SQUID. The effects of various parameters, such as the membrane dimensions and flow rate through the unit, on the mass transport rates were elucidated through a parametric modeling study. The applicability of the methods to the production of polymeric beads and more complex particles was demonstrated; to create Janus structures, organic polymer solutions were dispersed as droplets in continuous aqueous phases, and the solvent was subsequently evaporated. The Janus particles consisted either of polymeric cores with magnetite nanoparticles clustered as islands on their surfaces, or of two phase-separated polymers, each constituting half of any given polymeric particle.

Novel nucleophilic ligands were synthesized from oleic acid conjugated with 2-mercaptoimidazole via a UV-initiated thiol−ene reaction, and by a condensation of trans-9,10-epoxystearic acid with 4(5)-imidazoledithiocarboxylic acid. Nanoparticles (NPs) with 10−100 nm Ag(0) or Co(0) cores were obtained by reduction of Ag+ or Co2+ by borohydride in N,N-dimethylformamide or aqueous solutions respectively. The NPs capped with oleic acid or 9,10-epoxystearic acids were further covalently bound to 2-mercaptoimidazole or 4(5)-imidazoledithiocarboxylic acid. The ligands and NPs functionalized with nucleophilic imidazole moieties enabled facile hydrolysis of paraoxon (O,O-diethyl O-(p-nitrophenyl) phosphate) by NPs in their aqueous media. The NPs acted as recoverable semiheterogeneous catalysts. The paraoxon hydrolysis was accelerated 10- to 50-fold by the formation of complexes between the imidazole-containing ligands or NPs with Co2+.