Thomas J. McCarthy, Ph.D. - US grants

The synthesis of new polymeric materials is proposed, using olefin matathesis and olefin metathesis polymerization catalysis. This work is intended to demonstrate whether these reactions are versatile routes to a range of molecular topologies and are useful in polymer interface applications. Block copolymers will be prepared by the metathesis of vinyl-terminated polymers, the use of polymeric chain-transfer agents and the sequential addition of two specific monomers to a metathesis polymerization. Graft copolymers will be synthesized by the cometathesis of cyclic olefins and cyclic olefin-terminated polymers (macromonomers). Macrocyclic polymers will be prepared by metathesis of divinyl-terminated polymers using a heterogeneous catalyst. Single polymer and copolymer networks will be prepared by metathesis of dicyclic-olefin-terminated polymers and cometathesis of cyclic olefins and a crosslinking agent. The development of a versatile crosslinking agent is an objective of this work as well. Star polymers will be prepared by cyclic oligomerization of cyclic olefin-terminated polymers. Gradient modulus materials will be prepared by varying the crosslink density across one dimension of macroscopic poly(alkenamer) objects. Catalytic adhesion processes for polymers will be developed using both poly(alkenamers) and cyclic olefin- surface-modified vinyl polymers, metals and metal oxides. Thin film coatings of poly(alkenamers) will be constructed by surface graft metathesis from modified metal, metal oxide, and vinyl polymer surfaces. This research uses innovative methods to produce a variety of new materials, including some that have new types of structure on the surfaces of polymers. The properties of these new materials should be of considerable interest.

This award from the Major Research Instrumentation Program will allow the University of Massachusetts to purchase a x-ray photoelectron spectrometer (XPS) with integrated Auger analysis. The instrument will significantly enhance the capabilities of Interface Analysis Laboratory at UMass by providing high-resolution surface analysis and depth profiling capabilities that are currently lacking. The facility is accessible to the UMass community as well as research personnel from the surrounding Five College Community that includes Smith, Mt. Holyoke, Amherst and Hampshire Colleges and local industry. The Interface Analysis Laboratory and its director play an instrumental role in the support of broadly funded research programs in the chemical biological and materials sciences and for training of graduate and undergraduate students at these and other institutions. Specific programs include assessment of composition, contamination, interfacial properties and growth mechanisms for metal and semiconductor multi-layer films deposited from supercritical fluids, characterizing the chemical composition of polymer surfaces and interfaces modified to control interfacial interactions, surface wetting and biocompatability and the rational design of constrained-geometry catalysts for olefin polymerization.

This award from the Major Research Instrumentation Program will allow the University of Massachusetts to purchase a x-ray photoelectron spectrometer (XPS) with integrated Auger analysis. In tandem, XPS and Auger spectroscopy provide precise information regarding the atomic and molecular composition of surfaces that is crucial for the development and application of the advanced materials that are fueling today's economy. These include the assessment of metal and semiconductor films for microelectronic and photonic devices, the characterization of modified surfaces for consumer and medical applications, and the characterization of catalysts for more efficient fuel and chemical production. The instrument will be housed in an open Surface Analysis Facility that is easily accessible to the UMass Campus as well as research personnel from the surrounding Five College Community that includes Smith, Mt. Holyoke, Amherst and Hampshire Colleges and local industry. The facility plays an instrumental role in the training of graduate and undergraduate students at these and other institutions.

This Nanoscale Interdisciplinary Research Teams (NIRT) project it to develop robust routes to produce high-density arrays of functional nanoscopic structures using nanoporous templates derived from diblock copolymer thin films. The diblock copolymer films used possess self-assembled cylindrical microdomains oriented normal to the surface of the film, with cylinder densities in excess of 1.0 x 10^12 /in^2. Selective degradation of the minor polymer block and cross-linking of the major block results in a polymer film having a high-density array of nanopores that serves as a template for the fabrication of functional arrays of nanoscopic structures. The project will expand the potential of this simple process by developing methods that give pore diameters ranging from the nanometer to the hundreds of nanometers. The research will advance the use of these templates to produce functional arrays of nanoscopic structures. This includes the use of metal electrodeposition in the template pores to produce ultrahigh-density arrays of magnetic nanowires for magnetic storage applications. The nanopore array can be patterned laterally using electron-beam lithography, to create magnetic nanowires and nanoparticle electron-transport studies. The nanoporous arrays will also be used as electrochemical nanoelectrode arrays, as reactive-ion-etching masks for silicon technology, and to produce glass nanopillars.

The project provides several unique educational opportunities including REU, RET, an interdepartmental nanoscience course, biweekly interdisciplinary meetings, and a technology-training program based on interactive digital video. This project integrates efforts from the academic and industrial sectors, with collaborations from national laboratories and international groups.

The Polymer Science and Engineering Department of the University of Massachusetts-Amherst (Umass) is supported by the Chemistry Division, the Division of Undergraduate Education, and the MPS Office of Multidisciplinary Activities under the "Research Sites for Educators in Chemistry" (RSEC) program. The Prinicipal Investigator,. Thomas McCarthy is joined by Sandra Burkett of Amherst College, Wei Chen of Mount Holyoke College, and Kate Queeney of Smith College. This Western Massachusetts RSEC will integrate their research efforts. The planned research themes are (1) rational heterogenation of homogeneous catalyst, (2) molecular imprinting of polymeric materials, (3) surface modification to control wettability and biocompatibility, and (4) control of protein adsorption through chemistry and topography. To expand the RSEC, the program will focus its attention on nine other two- and four-year institutions in the local area. One of the goals of this RSEC is to increase the number of undergraduate chemistry majors at the participating institutions by injecting polymer and materials chemistry into existing courses at all levels, and by developing a one-semester course in polymer chemistry complete with notes and instructor's guide. Central to the formation of these collaborations is a series sabbaticals, and summer research appointments for faculty and undergraduate students at the four core institutions. This RSEC will be managed by a Director and an Advisory Board made up of representatives from each participating institution. There will also be an Executive Advisory Board made up of administrators from the institutions and outside experts in polymer research.

Research Sites for Educators in Chemistry bring together the faculty of participating two-year colleges, baccalaureate colleges, and master's universities with faculty at research universities within a geographic region, for the purpose of enhancing the research and educational opportunities for all participants. Academic and research institutions provide abundant opportunities where individuals may concurrently assume responsibilities as researchers, educators, and students, and where all can engage in joint efforts that infuse education with the excitement of discovery and enrich research through the diversity of learning perspectives. RSECs such as this one at the University of Massachusetts-Amherst provide mechanisms for disseminating the knowledge, skill, practices and ethics of research to a broader community, including those from underrepresented groups; assist in developing viable, sustainable research programs at participating institutions; and involve faculty and students at the participating institutions with a broader cross-section of faculty and students.

TECHNICAL AND NON-TECHNICAL ABSTRACT

This award provides partial support for travel of U.S. participants to the 2010 International Symposium on Polymer Chemistry (PC 2010). This meeting will be held in Suzhou, China, June 2 - June 5, 2010. An attendance of 300 is expected including 40 U.S. participants from diverse backgrounds. The technical scope of PC 2010 is intentionally broad to provide a forum that brings together leading and young scientists from academic institutions, governments and industries around the world to discuss the emerging and multi-disciplinary frontiers of polymer science. Five general research areas that encompass the frontiers of polymer chemistry were selected to attract participation from a broad range of disciplines: (1) polymer synthesis, (2) macromolecular architecture and supramolecules, (3) functional polymers for photonics, electronics and optoelectronics, (4) bio-related and medical polymers, (5) structure and characterization of polymers.