Reports: AC5

48100-AC5 Adsorption, Diffusion and Exchange Studies in Single-File Nanotube Materials for Gas Separations Using Hyperpolarized NMR Methods

Clifford R. Bowers, University of Florida

The PRF grant has provided funding for maintaining the infrastructure, supporting students, and repairing instrumentation in my laboratory. The PRF funding came at a time of critical need. The funds were used to support 2 graduate students and 2 undergrads.

Provision of a support to Chi-Yuan Cheng during Summer 2008 allowed him to complete the hyperpolarized NMR tracer exchange studies in the L-alanyl-L-valine and gallium wheel nanotubes, exactly as described in the ACS PRF proposal. It allowed Chi-Yuan to focus on completing his Ph.D. dissertation. His excellent experimental results, which are a direct result of PRF support, led to following three publications:

· Cheng, C.Y., J. Pfeilsticker, and C.R. Bowers, Dramatic enhancement of hyperpolarized xenon-129 2D-NMR exchange cross-peak signals in nanotubes by interruption of the gas flow. JACS, 2008. 130(8): p. 2390-2391.

· Cheng, C.-Y. and C.R. Bowers, Observation of Single-File Diffusion in Dipeptide Nanotubes by Continuous-Flow Hyperpolarized Xenon-129 NMR ChemPhyschem, 2007. 8(14): p. 5.

· Cheng, C.Y. and C.R. Bowers, Direct observation of atoms entering and exiting L-Alanyl-L-valine nanotubes by hyperpolarized xenon-129 NMR. JACS, 2007. 129(45): p. 13997-14002.

In addition, a four paper has been submitted:

· Cheng, C.Y.;  Stamatatos, T.C.; Christou, G.; and C.R. Bowers, Modes of Xenon Diffusion through Supramolecular Nanotubes of Gallium Molecular Wheels of Two Different Diameters, submitted to JACS, September 2009.

Cheng is now a postdoctoral research fellow with Prof. Song-I Han at the University of California, Santa Barbara.

A fifth paper presenting Cheng’s hyperpolarized 2D NMR exchange kinetic study on the gallium wheel nanotubes is in preparation. We expect it will be submitted sometime this Fall.

The ACS PRF grant funding has also provided research opportunities to several undergraduate students. It also was used to support an entering 1st year graduate student, Chris Akel, for the 2nd half of the Summer 2009.  Akel has joined my research group and is working on a research project described in my PRF proposal.

In addition, the results obtained from the PRF grant have been included as preliminary data in a full proposals submitted to NSF:

C.R. Bowers (PI) and S. Vasenkov (co-PI, UF Chem. Eng.), Understanding the Interrelationship between single-file diffusion and molecular exchange near nanochannel openings by xenon-129 nuclear magnetic resonance, proposal submitted to the NSF, Division of Chemistry (Physical Chemistry Program), $367,384 (submitted July 2008, notice of declination received July 2009).

C.R. Bowers (PI) and S. Vasenkov (co-PI, UF Chem. Eng.), Inducing molecular single file diffusion by co-adsorption in one-dimensional channels for gas separations and catalysis, proposal submitted to the NSF, Division of Chemistry (Physical Chemistry Program), $532,784 (submitted July 2009, pending review).

In addition, the following lecture invitations,  on topics directly related to the grant project, were received/presented:

· Single-file versus Fickian molecular diffusion and exchange in nanotube systems, Xenon NMR in Materials (XEMAT), Oulu, Finland, June 2009, invitation received.

· Xe diffusion and exchange in Ga10 and Ga18 wheel nanotubes: A hyperpolarized xenon-129 NMR study, Symposium on Magnetic Resonance and Biomolecular Mimetics &15th National Magnetic Resonance Society Meeting, Indian Institute of Chemical Technology, Hyderabad, India, February 2-5, 2009, invitation received with all expenses covered. 

· Kinetics of exchange and single-file diffusion of Xe in the nanochannels of the Ga10 wheel and AV: A hyperpolarized xenon-129 NMR study, Rocky Mountain Analytical Conference, NMR Symposium, Breckenridge, Colorado, July 27-31, 2008.

· Kinetics of exchange and single-file diffusion of Xe in the channels of the Ga10 wheel and other nanotube materials, Meeting of the Florida Chapter of the American Chemical Society (FAME), Christou Florida Award Symposium, May 9-10, 2008.