Center for the Integration of 

   Nanoscale COmponents

NSF-DMR 0210247

One-, Two-, and Three-dimensional Superstructured Materials from Well-defined, Complex Nanoscale Components

We propose to develop synthetic strategies and characterization protocols for the production and study of one-, two- and three-dimensional superstructures composed of stabilized nanoparticle assemblies. Our synthetic approach involves the systematic ordering, in solution and on substrates, of crosslinked assemblies of copolymers, as robust core-shell building blocks, to manufacture 1-dimensional meso-scale (~100 nm to ~1 mm), 2-dimensional micro-scale (~1 mm to ~100 mm) and 3-dimensional macro-scale (>100 mm) objects, each comprised of nanoscopic building blocks. The result will be the creation of entirely unique composite morphologies that are not accessible in the phase diagrams of the copolymers directly. This strategy mimics the control of chemistry at the nanometer scale that is currently the exclusive province of living systems.

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Prof. Karen L. Wooley

Washington University - St. Louis

314-935-7136

KLWooley@artsci.wustl.edu

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Our research efforts focus upon the development of synthetic methodologies for the preparation of well defined shell crosslinked knedel-like (SCK) polymer nanoparticles.  Through collaborative activities associated with this NIRTeam, we are able to advance procedures for the physical and chemical manipulation/assembly of the SCKs, and to perform rigorous characterization of their properties.

Dr. Craig Hawker

IBM - Almaden Research Laboratory

408-927-2377

hawker@almaden.ibm.com

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The renaissance of research activity in the area of polymer science is a direct result of the central importance of polymers in a wide variety of technology driven applications.  For example, the growing demand for functionalized soft materials with well-defined structures in nanoscale applications has lead to a dramatic increase in the development of procedures that combine architectural control with flexibility in the incorporation of functional groups.  In collaboration with other researchers my group at IBM has developed methods for controlling the length and dispersity of polymer chains through living free radical and living ring opening procedures.

The synthesis and application of 3-dimensional macromolecules with defined size and shape has also attracted significant attention in recent years with further refinement of traditional methods as well as novel strategies for their preparation being developed at IBM in the areas of dendrimers, nanoparticles and other complex macromolecular architectures.  One of the driving forces for this interest has been the realization that functionalized 3-dimensional polymers can be considered as building blocks for a variety of nanotechnological applications, ranging from vectors for drug and DNA delivery systems to various applications in information technology.  This included nanopatterned thin films, templating agents for nanoporous microelectronic materials, and in novel storage concepts such as Millipede.

Prof. Tomasz Kowalewski

Carnegie Mellon University

tomek@andrew.cmu.edu

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I love AFM.

Prof. Michael E. Mackay

Michigan State University

517-432-4495

mackay@msu.edu

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In my research, I use nanoparticles to manipulate the properties of polymers. We have found that nanoparticles will reduce the viscosity of polymer melts which is an enabling technology for nanocomposites. The final material properties are of interest too and they are enhanced. Nanoparticles are also used to stabilize thin films for use in sensors, optical devices, fuel cells or even adhesives. Finally we use nanoparticles to make the next generation data storage devices similar to the Millipede developed by IBM. Support from the NSF (CTS-0296166, NIRT-0210247), ACS-PRF, Sandia National Laboratories, Argonne National Laboratory and Dow Chemical Company is gratefully acknowledged.

Prof. Jill Pasteris

Washington University - St. Louis

314-935-5434

pasteris@levee.wustl.edu

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I use polarized-light optical microscopy and laser Raman microprobe spectroscopy to characterize minute volumes of solids (including minerals), liquids, and gases of geological interest.  Most of my recent research centers around the chemistry and mineralogy of biological mineralization, i.e., biologically induced development of nano-scale composites between organic (typically proteins) and inorganic (minerals) materials.  Of particular interest to my group is bone and its calcium phosphate mineral component, apatite.  With our CINCO collaborators, we have been investigating the effects of the presence of nanoparticles on the crystallization of simple ionic solids, e.g., NaCl.  Other members of my group, John Freeman and Brigitte Wopenka, additionally apply IR spectroscopy and laser scanning confocal fluorescence microscopy to these issues.

Prof. Darrin Pochan

University of Delaware

302-831-3569

pochan@udel.edu

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By working closely with our CINCO colleagues, the Pochan lab is developing self-assembly systems to build complex structures spanning the nano through microscale.  Specifically, amphiphilic block copolymers are being designed and synthesized in order to form novel structures in dilute solution.  Importantly, the polyelectrolytic, charged character of the copolymer hydrophilic block allows us to use biophysical tools in order to influence the self-assembly, e.g. the use of divalent counterions in order to make micelles self-attractive.  The combination of biological and synthetic polymer molecular tools thus allows new areas of self-assembly to be explored.  We bring expertise in transmission electron microscopy, laser scanning confocal microscopy, and neutron/x-ray scattering to the CINCO team.

Prof. Jacob Schaefer

Washington University - St. Louis

314-935-6844

schaefer@wuchem.wustl.edu

web page

We are using magic-angle spinning solid-state NMR to measure dipolar couplings between spins.  These couplings translate into accurate distance measurements on nano-materials that are not suitable for either solution NMR or diffraction experiments. The figure shows ¹³C-¹⁹F dipolar dephasing (S/S₀), which is proportional to dipolar coupling, for two fifth-generation poly(benzyl ether) dendrimers with ¹³C-labeled methylene carbons in the third (solid symbols) or fifth (open symbols) generations, with (circles) or without (squares) 10-fold dilution by homogeneous mixing by an unlabeled fifth-generation dendrimer.  The dotted lines show the calculated dephasing for an isolated ¹³C-¹⁹F pair as a function of the internuclear distance.  These calculations provide a convenient set of rulers and are not attempts to fit the experimental data.  The rulers show that in the solid state, the third-generation labels are about as far from the center of the dendrimer as the fifth-generation labels, which is not what is usually shown in cartoon representations of dendrimers.