The NMR facility is a service and research laboratory operated by and for the Department of Chemistry at Indiana University. The laboratory performs and assists in magnetic resonance spectroscopy activities that further the research goals of departmental faculty, post-doctoral fellows, students, and staff. The following report summarizes the service and research activities of the NMR Facility during 1999.

The NMR facility is proud to announce the addition of a new solid state NMR instrument. Through a grant from the NSF and matching funds from the College of Arts and Sciences, principal investigators professors Zwanziger, Caulton and Chisholm and scientist Werner-Zwanziger have purchased a Bruker 400 MHz NMR instrument for use by the department. This instrument is optimized for the study of solids. Installation of the instrument began in September 1999. The spectrometer is set up to acquire spectra of protons, fluorine, and other nuclei resonating at lower frequencies. It can do Magic Angle Spinning at speeds up to 35 kHz. A special feature is its capability to perform experiments on three nuclei simultaneously such as ¹H/¹³C/¹⁹⁵Pt correlations. Users from the organic, inorganic and physical chemistry have already made ample use of the instrument.

In addition, the NMR facility oversaw the donation, transport and installation of a Gemini NMR spectrometer operating at a 200 MHz ¹H Larmor frequency for the teaching facilities. DuPont de Nemours & Co. Inc. through Dr. Greg Urov, a former PHD student of Professor Peters, donated this instrument to the department. This instrument gives students of various classes hands-on experience in modern NMR spectroscopy.

The NMR Facility includes the following NMR spectrometers dedicated for liquid samples:

• Varian Unity^INOVA spectrometer operating at a 500 MHz ¹H Larmor frequency (I500)
• Varian Unity^INOVA spectrometer operating at a 400 MHz ¹H Larmor frequency (I400)
• Varian VXR-Unity spectrometer operating at a 400 MHz ¹H Larmor frequency (VXR400)
• Varian Gemini-2000 spectrometer operating at a 300 MHz ¹H Larmor frequency (Gem300)

In addition the NMR Facility operates the new spectrometer dedicated for solid samples:

• Bruker Avance spectrometer operating at a 400 MHz ¹H Larmor frequency (NMRSS1)

In conjunction, four Sun workstations, one SGI workstation, and two Windows-NT workstations provide processing, simulation, and administrative capabilities in the NMR Facility laboratory. A variety of probes are available for the observation of all possible nuclei and for conducting a wide variety of multinuclear experiments.

• two-dimensional experiments for the determination of biochemical structures (Novotny group)
• highly resolved two-dimensional experiments for analyses of polymer compositions (Chisholm group), of paramagnetic molecules (Christou group), and of metal complexes (Caulton group)
• surface studies of salts (Ewing group)
• experiments observing ¹¹B (Todd group), ¹⁷O (Caulton group), ²⁰⁷Pb (Caulton group), ⁹³Nb (Chisholm group), ⁵¹V (Christou group), ¹¹⁹Sn (Chisholm group), ²H (Christou, Caulton groups), and ²⁹Si (Caulton group)
• 35Cl-hemoglobin binding studies (Prange Group, Medical Sciences)
• solid state NMR experiments on orientation correlations in borate glasses (Zwanziger group)
• alignment studies in the solid and liquid crystalline state of Nickel and Zinc porphyrines (Chisholm and Zaleski groups)
• solid state experiments on solid/gas reactants (Caulton group)
• pulse sequence development for studies on phosphite glasses, conducting polymers and glass ceramics (Zwanziger group)

Publications

Chisholm, M.H., Iyer, S.S., McCollum, D.G., Pagel, M., & Werner-Zwanziger, U. Microstructure of Poly(lactide). Phase-Sensitive HETCOR Spectra of Poly(meso-lactide), Poly(rac-lactide) and Atactic Poly(lactide). Macromolecules, 32, 963-973, (1999).

Chisholm, M.H., Crandall, J.K., McCollum, D.G., & Pagel, M. Concerning the Mechanism of Ring-Opening polymerization by Coordinate Catalysts: The 2D Homonuclear J-Resolved Spectrum of Poly(cyclohexene oxide). Macromolecules, 32, 5744-5746 (1999).

Chen, P., Werner-Zwanziger, U., Wiesler, D., Pagel, M., &Novotny, M.V. Mass Spectrometric Analysis of Benzoylated Sialooligosaccharides and Differentiation of Terminal a 2à 3 and a 2à 6 Sialogalactosylated Linkages at Subpicomole Levels, Anal. Chem., 71, 4969-73 (1999).

Werner-Zwanziger, U., Brown, M.E., Chaney, J.D., Still, E.J., &Hollingsworth, M.D. Deuterium NMR Studies of Guest Motions in Urea Inclusion Compounds of 1,6-Dibromohexane with Analytical Evaluation of Spectra in the Fast Motion Limit, Appl. Magn. Reson. 17, 265-81 (1999)

Hollingsworth, M.D, Werner-Zwanziger, U., Brown, M.E., Chaney, J.D., Huffman, J.C., Harris, K.D.M., & Smart, S.P. Spring-Loading at the Molecular Level: Relaxation of Guest-Induced Strain in Channel Inclusion Compounds, J. Am. Chem. Soc., 121, 9732-33 (1999)

Zidek, L., Stone, M.J., Lato, S.M., Pagel, M.D., Miao, Z., Ellington, A.D., & Novotny, M.V. NMR Mapping of the Recombinant Mouse Major Urinary Protein I Binding Site Occupied by the Pheromone 2-sec-Butyl-4,5-dihydrothiazole. Biochemistry, 38, 9850-9861 (1999).

Coalter III, J. N., Bollinger, J. C., Huffman, J. C., Werner-Zwanziger, U., Caulton, K. G., Davidson, E R., Gérard, H., Clot, E., & Eisenstein, O. Coordinated carbenes from electron-rich olefins on RuHCl(PPri3)2, New Journal of Chemistry, 24, 9-26 (2000). in press

Joo, C., Werner-Zwanziger, U., & Zwanziger, J. W. The boroxol ring fraction in boron trioxide glass, J. Non-Cryst. Solids, in press.

Joo, C., Werner-Zwanziger, U., & Zwanziger, J. W., Anisotropy-Correlated Spectroscopy of Quadrupolar Nuclei, Solid State NMR, in press.

Joo, C., Werner-Zwanziger, U., & Zwanziger, J. W., The boroxol ring fraction in boron trioxide glass, Proceedings of the 3^rd International Conference on Borate Glasses and Liquids, in press.

Goodman, J.L., Pagel, M.D., & Stone, M.J., Relationships between Protein Structure and Dynamics from a Database of NMR-Derived Backbone Order Parameters. J. Mol. Biol., in press.

Hollingsworth, M.D., Brown, M.E., Werner-Zwanziger, U., Hillier, A.C., Chaney, J.D., Still, E.J., & Vanecko, J.A., Superstructure Control of Shape and Ferroelasticity of Urea Inclusion Compounds, in Self-Assembly in Synthetic Chemistry, Wuest, J.D., ed., NATO ASI Ser., Kluwer Academic Publishers, Dordrecht, The Netherlands, submitted for publication.

Proton and Carbon NMR Studies of Pure and Plasticized Poly(Vinyl Chloride), Werner-Zwanziger, U., Pfaadt, M., Wilhelm, M., Pawelzik, U., & Spiess, H.W., 40^th Experimental Nuclear Magnetic Resonance Conference, Orlando, Florida, 2/28-3/5/99.

MAG RES, a Web-Based Spectrometer Reservation & Scheduling System, Association of Managers of Magnetic Resonance Laboratories Annual Meeting, Orlando Fl., 3/1/99.

U. Werner Zwanziger was promoted to the faculty rank of assistant scientist.

J.D. Frey was listed as a "Local Support Provider" for the Dept. of Chemistry by UITS

J.D. Frey completed the necessary classes and exams to be rated as a Unix Administrator by Indiana University.

Summary of Facility Services

Profile of Spectrometer Utilization
The NMR Facility is available 24 hours per day, each day of the year, for collaborative or independent use by trained researchers. The Graph Gallery shows the utilization of each spectrometer from Jan. 1 to Dec. 31, 1999, in several formats. The following observations (shown in bold) and interpretations are derived from the Graph Gallery:

• Utilization of the I500 is extremely high. The I500 is efficiently used by the biochemists for large blocks of time.
• Inorganic chemists dominate utilization of the Gem300 and I400. Organic chemists dominate utilization of the VXR400. Biochemists dominate utilization of the I500. Data stations were used by a variety of research interests. The utilization of each spectrometer matches the NMR Facility utilization plan. Utilization of the VXR400 by inorganic chemists has not impacted upon VXR400 availability for organic chemists. Utilization of the I400 by organic chemists has not impacted upon I400 availability for inorganic chemists.

Notable services

• The Staff offered in the spring and fall semester a series of "NMR meetings" discussing the practical aspects and background of NMR spectroscopy. The Staff presented two lectures in C502 (Inorganic Spectroscopy) covering the basic procedures for one and two dimensional experiments, one about the use of auxiliary simulation programs and two lectures in C503 (Spectrometric Methods of Structure Determination) covering the qualitative theory and practice of one-dimensional and two-dimensional NMR spectroscopy.

• The Staff assisted in the acquisition, transport and installation of a donated 200MHz NMR instrument for the teaching laboratory. Furthermore, the staff performed extensive repairs until the instrument now operates well.
• The Staff mediated the sale of the T60 and EM390 continuous wave spectrometers.
• The Staff consulted with Dr. Maggie Hupcey of the Sabin Corp., Bloomington, IN and ESPE, Germany concerning the NMR spectroscopy of polymers.
• MAG RES, the web-based magnet reservation and scheduling system, was distributed to 24 other national and international NMR Facilities.
• MAG LOG, the spectrometer accounting system, was distributed to 3 other NMR Facilities.

Summary of Facility Developments
Spectrometer Improvements

• The Varian spectrometer software was upgraded to VNMR v6.1b on all Varian spectrometers and workstations (except the I500 spectrometer, which was upgraded to VNMR v6.1a).
• All spectrometers and workstations were Y2K-compliant and made the Year 2000 transition without problems.

Acquisition of a New Spectrometer

• Evaluation and negotiations with the vendors for the new solid state NMR instrument progressed during the spring semester 1999. The set-up of the instrument with its various probes followed during the fall and are still ongoing (as of January 2000). The new instrument required a lot of customization of experimental conditions and of administrative procedures.

Laboratory Improvement

• The Staff collaborated with Dr. Marty Berliner to develop VNMRPlot. This software application can be used to produce plots of NMR spectra with customized properties. VNMRPlot was submitted to Varian for their consideration. Subsequently, VNMRPlot has been distributed to Varian NMR user community as a standard component of Varian’s software distribution.
• The VXR400 workstation was upgraded to the Solaris 2.5 operating system.
• The NMRSUN1 datastation, a Sun IPX workstation, was replaced by NMRSUN5, a Sun Sparc20workstation. More memory has been added to various data-stations for increase performance. A newer monitor was placed at the VXR400 for improved viewing of experimental runs.
• A PC-based CD burner has been added to the Facility for improved data archiving.
• A chemical spill kit was placed in the general lab area next to the fire extinguisher and first aid kit.
• The Web pages were updated with various help and "how to" items in the "User’s Guide".

Continuing Projects

• The installation of the departmental solid-state NMR spectrometer will be continued with several probes and features still not available yet.
• J-Design, a JAVA-based "what-you-see-is-what-you-get" plotting tool developed by Varian will be tested and implemented for improved printing capabilities.
• MAG RES will be improved:

1. add signup possibilities for the new solid state NMR instrument
2. add automatic reservation of recurring periods (e.g., recurring "open hours)
3. improve password security

• Automate billing for the new solid state NMR instrument.
• Provide advanced training for in-depth working knowledge Of NMR techniques

NMR Facility Laboratory Chemistry C237

Phone: (812)-855-6492
Fax: (812)-855-8300
Address: Chemistry Building
Indiana University
Bloomington, IN 47405-4001
Email: chemnmr@indiana.edu
URL: http://nmr.chem.indiana.edu

NMR Facility Staff
NMR Facility Director Marty Pagel
Phone: (812)-855-4478
Location: Chemistry C237C
Email: mpagel@indiana.edu
URL: http://nmr.chem.indiana.edu/~mpagel

NMR Facility Manager Ulrike Werner-Zwanziger
Phone: (812)-855-4629
Location: Chemistry C237D
Email: uwerner@indiana.edu
URL: http://nmr.chem.indiana.edu/~ulli

NMR Operations Specialist Jeff Frey
Phone: (812)-855-6492 (general facility phone)
Location: Chemistry C237B
Email: jdfrey@indiana.edu
URL: http://nmr.chem.indiana.edu/~jdfrey

NMR Computing Systems Specialist Ken DeHart
Phone: (812)-855-8450
Location: Chemistry C238E
Email: dehartk@indiana.edu
URL: http://nmr.chem.indiana.edu/~dehart

The NMR Facility 1999 Annual Report is also available at http://nmr.chem.indiana.edu/pubs/99_annual_report/

About the Cover

These spectra are the first solid-state NMR spectra taken on the new Bruker Avance NMR spectrometer in the departmental NMR Facility. Presented are room temperature ¹³C NMR spectra of a Nickel Porphyrine complex prepared by Brian Pate (Chisholm/Zaleski groups). The top two traces show spectra under magic angle sample spinning at two different spinning speeds. Spinning sidebands indicated by stars move with the spinning frequency. The bottom trace shows the spectrum obtained under static sample conditions. Upon heating, this material undergoes a liquid crystalline phase transition. The goal of this research is to determine the alignment of the liquid crystalline molecules from the knowledge of the chemical shift tensors in the rigid solid phase. The doublets prove the existence of non-equivalent carbon sites in the solid state.

1999 Graph Gallery

Data for the Graph Gallery was derived from NMR Facility accounting records from December 31, 1998 to November 30, 1999 (Dec 31, 1998 was included with Jan. 99). These records were automatically generated from the spectrometer & datastation login/logout processes. All data is accurate to within 1 minute.