1. Nanostructured Polymers for Brønsted and Lewis Acid Catalysis via Monomer Self-assembly Douglas Gin (University of Colorado at Boulder) DMR-0111193 Nanostructured, heterogeneous catalysts such as inorganic zeolites often afford substrate size discrimination, enhanced activity, and high reaction selectivity because of their uniform porous microstructures. However, inorganic catalysts lack processability and the ability to incorporate a wide range of catalytic groups. We recently synthesized the first example of a nanostructured, solid acid polymer resin using H-bonded acidic lyotropic liquid crystal monomers. We just tested this LLC sulfonic acid catalyst against an amorphous acid resin (Amberlyst) in the sequential diesterification of phthalic anhydride to form dioctyl phthalate, an important plasticizer. The LLC resin afforded a faster initial rate and better yields in the rate- determining second esterification step compared to Amberlyst-15. We also discovered a way to form LLC resins containing chiral Diels-Alder catalysts via acid-induced LLC assembly. Xu, Nguyen, Elliott, Gin, AIChE J. 2005, in press. Pecinovsky, Nicodemus, Gin, Chem. Mater. 2005, submitted. ~ 1 nm Fig. 1. Enhancement of 2nd step of DOP synthesis by LLC acid resin Fig 2. Acid-induced LLC assembly of chiral catalyst monomers DOP 2nd “Step” Percent Yield of DOP 35–40% increase in yield over first 5 h compared to Amberlyst ~ 38% increase in avg initial rate compared to Amberlyst-15 LLC resin

2. Education: Currently, two graduate students are being partially supported by this NSF grant: Yanjie Xu (ChE, 4th year) and Mr. Cory Pecinovsky (Chem, 3rd year). With partial support from this grant, one graduate student has completed his Ph.D. degree: Dr. Alan Sentman (Polymer Soutions, Inc.); one postdoctoral researcher has been trained: Dr. Weiqiang Gu (Waters Corp.); and one REU undergraduate student has been supported: Mr. Cory Pecinovsky (Abilene Christian College, prior to entering grad school at CU). This past year, I taught Physical Organic Chemistry for first-year Chem graduate students, and a joint undergraduate/graduate Polymer Engineering course in ChE. As a 50/50 faculty member in both the Chem and ChE departments, I have been successfully integrating aspects of both disciplines into my courses, so that the students receive cross-disciplinary training. Outreach: Several RET researchers have worked in my labs over the past 3 summers in a joint effort with the CU Boulder Liquid Crystal Materials Research Center's outreach program. Last year, an undergraduate summer researcher, Mr. Garret Nicodemus, was supported from this grant. The research Garret did last summer is an important part of a Chemistry of Materials manuscript currently in review, and he is second author on this paper. Currently, a part- time undergraduate researcher, Lauren Kimiele, is working on a new joint project in our labs this summer. Other prior outreach activities under this grant included a cooperative project with the Colorado Commission on Higher Education in 2003. Samples of our LLC acid resin catalysts are also currently being evaluated by Akzo Nobel USA and (formerly) Atofina USA for catalysis of some of their processes of interest. Nanostructured Polymers for Brønsted and Lewis Acid Catalysis via Monomer Self-assembly Douglas Gin (University of Colorado at Boulder) DMR-0111193