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Amphiphilic polymers based on modular norbornene derivatives exhibit good antibacterial activities and high selectivity for bacteria versus red blood cells. The study showed the preparation of fully synthetic high molecular weight polymers that mimic the activities of host-defensive peptides in the absence of a specific secondary structure.

In the study, cadmium selenide nanoparticles are stabilized with phosphine oxide and then used in the polymerization of cyclic olefins. This is done by ruthenium-catalyzed ring-opening metathesis polymerization.

The synthesis of rac-Me2Si(2-SiMe3-4-CMe3C5H2)2YR or (rac-BpYH)2 provides the firstiso-specific, single component Ziegler-Natta polymerization catalyst. (rac-BpYH)2 is obtained by addition of YCl3(THF)3 to LiBp, followed by deprotonation and removal of lithium chloride and tetrahydrofuran. The catalystis shown to effectively induce the polymerization of propylene, 1-butene, 1-pentene and 1-hexene into medium molecular weight (4,200-24,000) polymers.

Amphiphilic cationic polynorbomene derivatives, soluble in water, were prepared from modular norbornene monomers, with a wide range of molecular weights (Mn = 1600-137 500 g/mol) and narrow polydispersities (PDl = 1.1-1.3). The antibacterial activity determined by growth inhibition assays and the hemolytic activity against human red blood cells were measured and compared to determine the selectivity of the polymers for bacterial over mammalian cells. The effects of monomer repeat unit hydrophobicity and polymer molecular weight on antibacterial and hemolytic activities were determined. The hydrophobicity of the repeat unit was observed to have dramatic effects on antibacterial and hemolytic activities. Lipid membrane disruption activities of the polymers was confirmed by measuring polymer-induced dye leakage from large unilamellar vesicles. By tuning the overall hydrophobicity of the polymer through random copolymerizations of modular norbornene derivatives, highly selective, nonhemolytic antibacterial activities were obtained. For appropriate monomer composition, selectivity against bacteria versus human red blood cells was determined to be over 100. [ABSTRACT FROM AUTHOR]

Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when two different metallic species are mixed at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesized with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy, and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods was then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence dependence in both surface structure and surface composition. Replica exchange with solute tempering molecular dynamics simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be leveraged for rational bimetallic nanoparticle design using peptide-enabled approaches.

Polystyrene- block -poly(maleimide pentafluorophenyl ester- co -styrene)- block -poly(ethylene oxide) with an o -nitrobenzyl ester junction was synthesized by "one-step" RAFT polymerization. Highly ordered and locally reactive nanoporous thin films were obtained from the photocleavable triblock copolymer after spin coating, solvent annealing, UV exposure, and washing with methanol/water to remove the minor block PEO. The local reactivity in the thin films was demonstrated by fabrication of iron oxide nanotori after post-modification with an amino-functionalized ferrocene and treatment with oxygen plasma.

Hybrid conjugated polymers containing carborane directly bonded in the aromatic backbone repeat structure have interesting electronic bonding structures and are potentially useful new materials in organic electronics. Conjugated polymers based on o-carborane are particularly interesting for applications in sensing and detection because of the cage's unique bonding scheme and its bent geometry. Poly(fluorene) containing o-carborane displays multiple emission pathways that can be modulated through interactions with small molecules. In this paper, we report that films of poly(fluorene) with o-carborane in the backbone function as vapochromatic photoluminescent sensors toward volatile organic molecules., (© 2011 American Chemical Society)

This work examines how the binding strength of surface-immobilized "stickers" (representative of receptors or, in nonbiological systems, chemical heterogeneities) influences the adhesion between surfaces that are otherwise repulsive. The study focuses on a series of surfaces designed with fixed average adhesive energy per unit area and demonstrates quantitatively how a redistribution of the adhesive functionality into progressively larger clusters (stronger stickers) increases the probability of adhesive events. The work employs an electrostatic model system: relatively uniform, negative 1 μm silica spheres flow gently over negative silica flats. The flats contain small amounts of randomly positioned nanoscale cationic patches. The silica-silica interaction is repulsive; however, the cationic patches (present at sufficiently low levels that the overall surface charge remains substantially negative) produce local attractions. In this study, the attractions are relatively weak so that multiple patches engage to capture flowing particles. Experiments reveal an adhesion signature characteristic of a renormalized random distribution when the sticker strength is increased at an overall fixed binding strength per unit area of surface. The form of the particle capture curves are in good quantitative agreement with a simple model that assumes only a fixed adhesion energy needed for particle capture. Aside from the quantitative details that provide a simple formalism for anticipating particle adhesion, this work demonstrates how increasing the heterogeneities in the surface functionality can cause a system to go from being nonadhesive to becoming strongly adhesive. Indeed, systems containing small amounts of discretized adhesive functionality are always more adhesive than systems in which the same functionality is distributed uniformly over the surface (the mean field scenario).

The synthesis of a novel silylcarborane acrylate monomer is reported as well as its application as an etch-resistant component for the formulation of imprint layers for UV nanoimprint lithography (NIL). By introduction of 10% by weight of the silylcarborane acrylate monomer into NIL resist formulations, the oxygen plasma etch rate of the resulting film was reduced by nearly a factor of 2. When used in NIL, the patterned resist layer had excellent oxygen plasma etch resistance, leading to effective image transfer to the underlying poly(hydroxyethyl methacrylate) lift-off layer. The latter allowed for the fabrication of metallic interdigitated electrode patterns via a NIL/lift-off process. This work demonstrates the robustness of silylcarborane-containing resists and paves the way for the investigation of new, high-resolution patterning methods.

Antimicrobial polynorbornenes composed of facially amphiphilic monomers have been previously reported to accurately emulate the antimicrobial activity of natural host-defense peptides (HDPs). The lethal mechanism of most HDPs involves binding to the membrane surface of bacteria leading to compromised phospholipid bilayers. In this paper, the interactions between biomimetic vesicle membranes and these cationic antimicrobial polynorbornenes are reported. Vesicle dye-leakage experiments were consistent with previous biological assays and corroborated a mode of action involving membrane disruption. Dynamic light scattering (DLS) showed that these antimicrobial polymers cause extensive aggregation of vesicles without complete bilayer disintegration as observed with surfactants that efficiently solubilize the membrane. Fluorescence microscopy on vesicles and bacterial cells also showed polymer-induced aggregation of both synthetic vesicles and bacterial cells. Isothermal titration calorimetry (ITC) afforded free energy of binding values (Delta G) and polymer to lipid binding ratios, plus revealed that the interaction is entropically favorable (Delta S>0, Delta H>0). It was observed that the strength of vesicle binding was similar between the active polymers while the binding stoichiometries were dramatically different.