Controlling surface mobility in interdiffusing polyelectrolyte multilayers.

The phenomenon of interdiffusion of polyelectrolytes during electrostatic layer-by-layer assembly has been extensively investigated in the past few years owing to the intriguing scientific questions that it poses and the technological impact of interdiffusion on the promising area of electrostatic assembly processes. In particular, interdiffusion can greatly affect the final morphology and structure of the desired thin films, including the efficacy and function of thin film devices created using these techniques. Although there have been several studies on the mechanism of film growth, little is known about the origin and controlling factors of interdiffusion phenomena.

Layer-by-layer assembly of all carbon nanotube ultrathin films for electrochemical applications.

All multiwall carbon nanotube (MWNT) thin films are created by layer-by-layer (LBL) assembly of surface functionalized MWNTs. Negatively and positively charged MWNTs were prepared by surface functionalization, allowing the incorporation of MWNTs into highly tunable thin films via the LBL technique. The pH dependent surface charge on the MWNTs gives this system the unique characteristics of LBL assembly of weak polyelectrolytes, controlling thickness and morphology with assembly pH conditions.

Patterning nanodomains with orthogonal functionalities: solventless synthesis of self-sorting surfaces.

simple method to fabricate a multifunctional patterned platform on the nanometer scale is demonstrated. The platform contains two reactive functional groups on the surface: one is an acetylene group which can be functionalized via click chemistry, and the other is an amine group which can also be functionalized by classic carbodiimide chemistry with N-hydroxysuccinimide (NHS). The click-active and amine surface could be obtained from polymer coating of poly(propargyl methacrylate) (PPMA) via initiated chemical vapor deposition (iCVD) and poly(allylamine) (PAAm) via a plasma polymerization process, respectively, utilizing commercially available monomers.

Controlling the morphology of side chain liquid crystalline block copolymer thin films through variations in liquid crystalline content.

In this paper, we describe methods for manipulating the morphology of side-chain liquid crystalline block copolymers through variations in the liquid crystalline content. By systematically controlling the covalent attachment of side chain liquid crystals to a block copolymer (BCP) backbone, the morphology of both the liquid crystalline (LC) mesophase and the phase-segregated BCP microstructures can be precisely manipulated. Increases in LC functionalization lead to stronger preferences for the anchoring of the LC mesophase relative to the substrate and the intermaterial dividing surface.

Stamped microbattery electrodes based on self-assembled M13 viruses.

The fabrication and spatial positioning of electrodes are becoming central issues in battery technology because of emerging needs for small scale power sources, including those embedded in flexible substrates and textiles. More generally, novel electrode positioning methods could enable the use of nanostructured electrodes and multidimensional architectures in new battery designs having improved electrochemical performance. Here, we demonstrate the synergistic use of biological and nonbiological assembly methods for fabricating and positioning small battery components that may enable high performance microbatteries with complex architectures.

Release of a model protein from biodegradable self assembled films for surface delivery applications.

Layer-by-layer (LbL) films have multiple features that make them attractive for drug delivery, including the potential to sequentially deliver growth factors from implantable medical devices or tissue engineering scaffolds. To date, however, characterization has been lacking for protein delivery from such films. Here, LbL polyelectrolyte films constructed with the model protein lysozyme and a hydrolytically degradable and biocompatible synthetic polycation are characterized.

Metal ion reactive thin films using spray electrostatic LbL assembly.

By using the spray-layer-by-layer (Spray-LbL) technique, the number of metal counterions trapped within LbL coatings is significantly increased by kinetically freezing the film short of equilibrium, potentially limiting interchain penetration and forcing chains to remain extrinsically compensated to a much greater degree than observed in the traditional dipped LbL technique. The basis for the enhanced entrapment of metal ions such as Cu2+, Fe2+, and Ag+ is addressed, including the equilibrium driving force for extrinsic compensation by soft versus hard metal ions and the impact of Spray-LbL on the kinetics of polymer-ion complexation. These polymer-bound metal-ion coatings are also demonstrated to be effective treatments for air filtration, functionalizing existing filters with the ability to strongly bind toxic industrial compounds such as ammonia or cyanide gases, as well as chemical warfare agent simulants such as chloroethyl ethyl sulfide.

Temperature-triggered reversible micellar self-assembly of linear-dendritic block copolymers.

Polymeric micelles based on a thermoresponsive linear-dendritic block copolymer were completely disrupted into unimers upon cooling the solution to a temperature below its LCST and reversibly regenerated upon heating again.

Effect of the layer-by-layer (LbL) deposition method on the surface morphology and wetting behavior of hydrophobically modified PEO and PAA LbL films.

We demonstrate that the surface morphology and surface-wetting behavior of layer-by-layer (LbL) films can be controlled using different deposition methods. Multilayer films based upon hydrogen-bonding interactions between hydrophobically modified poly(ethylene oxide) (HM-PEO) and poly(acrylic acid) (PAA) have been prepared using the dip- and spin-assisted LbL methods. A three-dimensional surface structure in the dip-assisted multilayer films appeared above a critical number of layer pairs owing to the formation of micelles of HM-PEO in its aqueous dipping solution.

Exponential growth of LBL films with incorporated inorganic sheets.

The fastest growth pattern of layer-by-layer (LBL) assembled films is exponential LBL (e-LBL), which has both fundamental and practical importance. It is associated with "in-and-out" diffusion of flexible polymers and thus was considered to be impossible for films containing clay sheets with strong barrier function, preventing diffusion. Here, we demonstrate that e-LBL for inorganic sheets is possible in a complex tricomponent film of poly(ethyleneimine) (PEI), poly(acrylic acid) (PAA), and Na(+)-montmorillonite (MTM).

Polyelectrolyte multilayers for tunable release of antibiotics.

Polyelectrolyte multilayers incorporating gentamicin were fabricated using layer-by-layer deposition. The multilayers could be precisely tuned with regard to dosage, and release rate under aqueous physiological conditions could be controlled. The films were demonstrated efficacious against Staphylococcus aureus and nontoxic toward murine osteoblasts MC3T3.

Influence of variations in liquid-crystalline content upon the self-assembly behavior of -based block copolymers.

A series of well-defined smectic side chain liquid-crystalline (LC) block copolymers with a low glass transition (Tg) siloxane block has been synthesized via anionic polymerization; these systems consist of a glassy polystyrene block and a unique low glass transition temperature LC block based on poly(vinylmethylsiloxane) to which six different LCs have been synthesized and attached. The synthesis techniques used provide systematic control over covalent LC side chain content, allowing for a range of morphologies to be obtained from a single block copolymer backbone during a one-step LC attachment reaction. Variations in the LC structure and content significantly affect the morphology of the LC mesophase, allowing the smectic-to-isotropic transition temperature to be tuned from room temperature up to 150 °C.

Solvent-assisted patterning of polyelectrolyte multilayers and selective deposition of virus assemblies.

We introduce a simple method to pattern electrostatic assemblies of viruses onto a polyelectrolyte multilayer. The increased mobility of weak polycation chains in the multilayer above a given thickness ensures the surface mobility of viruses required for spontaneous ordering of densely packed viruses atop polymeric patterns. To pattern the polyelectrolyte multilayer film, we employ a nonconventional patterning method known as solvent-assisted capillary molding for the first time on multilayer films, and demonstrate micrometer-scaled dense patterns of viruses, where the accessible feature size can be correlated by the length scale of virus and swelling property of underlying patterned polyelectrolyte multilayer.

Electroactive controlled release thin films.

We present the fabrication of nanoscale electroactive thin films that can be engineered to undergo remotely controlled dissolution in the presence of a small applied voltage (+1.25 V) to release precise quantities of chemical agents. These films, which are assembled by using a nontoxic, FDA-approved, electroactive material known as Prussian Blue, are stable enough to release a fraction of their contents after the application of a voltage and then to restabilize upon its removal.

Tumor-targeted gene delivery using molecularly engineered hybrid polymers functionalized with a tumor-homing peptide.

Before gene therapy can be used in clinical settings, safe and efficient DNA delivery systems must be developed to overcome a range of extra- and intracellular transport barriers. As a step toward the development of a modular, multifunctional gene delivery system to overcome these diverse barriers, we have developed a family of linear-dendritic "hybrid" polymers which contain functionalities for tissue targeting, minimization of nonspecific interactions, endosomal buffering, and DNA binding. Here, we demonstrate the rapid three-step, room-temperature, aqueous synthesis of hybrid polymers, as well as the functionalization of these polymers with a peptide targeting ligand that specifically binds to glucose-regulated protein-78 kDa (GRP-78), a clinically relevant tumor antigen identified in human cancer patients.

Anisotropic structure and transport in self-assembled layered polymer-clay nanocomposites.

Using the layer-by-layer (LbL) assembly technique, we create a polymer-clay structure from a unique combination of LbL materials: poly(ethylene imine), Laponite clay, and poly(ethylene oxide). This trilayer LbL structure is assembled using a combination of hydrogen bonding and electrostatic interactions. The films were characterized using ellipsometry, profilometry, X-ray photon spectroscopy, atomic force microscopy, scanning electron microscopy, wide-angle X-ray diffraction, grazing-incidence small-angle X-ray scattering, and electrochemical impedance spectroscopy (EIS).

Electrochemically enabled polyelectrolyte multilayer devices: from fuel cells to sensors.

With an ever-increasing need for thin, flexible and functional materials in electrochemical systems, the layer-by-layer (LbL) technique provides a simple and affordable route in creating new, active electrodes and electrolytes. The LbL technique, which is based upon the alternate adsorption of oppositely charged species from aqueous solution, possesses unprecedented control of materials selection ( polyelectrolytes, clays, nanoparticles, proteins), materials properties ( conductivity, glass-transition temperature) and architecture ( blends, stratified-layers, pores). These advantages make LbL assemblies excellent candidates for use in proton-exchange membrane and direct methanol fuel-cells, batteries, electrochromic devices, solar cells, and sensors.

Creating patterned carbon nanotube catalysts through the microcontact printing of block copolymer micellar thin films.

We report a route for synthesizing patterned carbon nanotube (CNT) catalysts through the microcontact printing of iron-loaded poly(styrene-block-acrylic acid) (PS-b-PAA) micellar solutions onto silicon wafers coated with thin aluminum oxide (Al(2)O(3)) layers. The amphiphilic block copolymer, PS-b-PAA, forms spherical micelles in toluene that can form quasi-hexagonal arrays of spherical PAA domains within a PS matrix when deposited onto a substrate. In this report, we dip a poly(dimethylsiloxane) (PDMS) molded stamp into an iron-loaded micellar solution to create a thin film on the PDMS features.

Amphiphilic linear-dendritic triblock copolymers composed of poly(amidoamine) and poly(propylene oxide) and their micellar-phase and encapsulation properties.

A novel amphiphilic ABA dendritic-linear-dendritic block copolymer consisting of poly(amidoamine) and poly(propylene oxide) has been synthesized. The solution-phase behavior of the block copolymer was studied as a function of the generation of the dendritic block, ionic strength, and solution pH. The triblock self-assembles in aqueous media to form stable micelles with CMC values ranging from 10(-6) to 10(-5) M.

Solution behavior of linear-dendritic rod diblock copolymers in methanol.

The solution behavior of spherical dendrimers as well as hybrid-linear dendritic diblock copolymers has been extensively studied, and the size, shape, and ability of these polymers to encapsulate small molecules have led to their comparison with traditional micelles. We have recently reported the synthesis of a new dendritic copolymer architecture, the linear-dendritic rod diblock copolymer, and in this work, we examine the solution behavior of these unique polymers in methanol at 25 degrees C, using dynamic light scattering and intrinsic viscosity measurements. The diblock copolymers consist of a linear poly(ethylene oxide)-poly(ethylene imine) diblock copolymer backbone around which poly(amido amine) branches have been divergently synthesized from the poly(ethylene imine) block.

Vesicular self-assembly of comb-dendritic block copolymers.

New amphiphilic comb-dendritic block copolymers were developed as building blocks that self-assemble into stable vesicular structures with narrow size distribution.