NMR Facility 1997 Annual Report

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)-856-4629 Location: Chemistry C237D Email: uwerner@indiana.edu. URL: http://nmr.chem.indiana.edu/~uwz NMR Operations Specialist Jeff Frey Phone: (812)-855-6492 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 1997 Annual Report is also available at

http://nmr.chem.indiana.edu/pubs/97_annual_report/

About the Cover
The two-dimensional Long-Range HETCOR spectrum of menthol provides correlations between protons and other nuclei that are separated by two or three bonds. The proton resonaces are homonuclear decoupled and should appear as singlets. The vertical projection to the left of the 2D spectrum shows excellent resolution. The horizontal traces display projections of the proton dimension both derived from the same experimental data. The lower trace was obtained through standard data processing methods; this trace shows poorly resolved peaks that do not match the true (homonuclear decoupled) resonances. The top trace was obtained after the data set was extended four-fold in the t1 dimension with linear prediction; this trace shows well-resolved peaks that match the true (homonuclear decoupled) resonances.

Linear Prediction can now be routinely applied to standard experiments in the NMR Facility. As shown here, this powerful technique is used to improve spectral resolution to reveal subtle effects in conformation and configuration. Linear Prediction is also used to halve the experimental acquisition time needed to study "routine" molecules that don’t require excellent resolution for analysis. Sufficient spectral signal-to-noise is required for linear prediction.

NMR Facility Department of Chemistry Indiana University 1997 Annual Report

Introduction

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 1997.

Summary of Facilities

The NMR Facility includes the following Varian NMR spectrometers:

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

In conjunction, three Sun workstations provide processing capabilities. A variety of probes are available for the observation of all possible nuclei and multinuclear experiments.

Summary of Research Activities

Research collaborations

Non-routine research collaborations include development of new NMR techniques or interpretation of spectra beyond daily interactions between Staff and Users. Research collaborations in 1997 include:

two-dimensional experiments for the determination of biochemical structures and conformations (Novotny group)
highly resolved two-dimensional experiments for analyses of polymer compositions (Chisholm group)
identification and structural determination of electrolysis products (Peters group)
solid-state NMR experimentation with polymers (Chisholm group)
one-dimensional diffusion measurements via pulsed-field NMR gradients (Zwanziger group)
binuclear ¹H-¹⁹F & ¹³C-³¹P and trinuclear ¹H-¹⁹F-³¹P & ¹H-¹⁹F-¹³C experiments (Caulton group)
experiments observing ¹⁵N (Zaleski group), ¹¹B (Todd group), ¹⁷O (Caulton group), ⁵⁷Fe (D. Linn, IPFW), 51V (Christou group), and ²⁰⁷Pb (Caulton group).
structure calculation of cross-linked peptides from NMR data (Daleke Group)

Publications

Baker, A., Zidek, L., Wiesler, D., Chmelik, J., Pagel, M., & Novotny, M.V. Reaction of N-Acetyl-Glycyl-Lysyl-Methyl Ester with 2-Alkenals: An Alternative Model for Covalent Modification of Proteins. Accepted Chem. Res. & Toxicol.

M.S. Mubarak, M. Pagel, L.M. Marcus, & D.G. Peters Formation of 2-(3’-Oxocyclohexyl)-2-cyclohexen-1-one via Reduction of 2-Cyclohexen-1-one with Electrogenerated Nickel (I) Salen. Accepted, J. Org. Chem., Feb 20 issue.

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 Dec. 31, 1996, to Nov 30, 1997, in several formats. The following observations (shown in bold) and interpretations are derived from the Graph Gallery:

Utilization of all spectrometers was highest for June & July. Therefore, the quench & re-energization of the Gem300 magnet during these months did not decrease productivity in the NMR Facility.

Utilization of the VXR400 decreased in September; VXR400 utilization increased in October & November. The departure of the Roush & Grieco groups after July caused a decrease in VXR400 utilization. Inorganic chemists were allowed to use the VXR400 on a trial basis in October and as a formal policy in November, compensating for the loss of the Roush & Grieco group utilization.

Utilization of the I400 increased in July through November. New probes were installed on the I400 in April and June, and new experiments for the I400, especially after U. Werner-Zwanziger joined the staff in June. Users began to take advantage of these capabilities in July.

Utilization of the I500 was highest during June, July, and August; utilization was very low in November. The Stone group made substantial use of the I500 from June to October; the Roush & Grieco groups used the I500 from January to July. I500 utilization was highest when all three of these groups used the I500 (June, July, & August); I500 utilization was lowest when none of these groups used the I500 (November).

The Gem300 and VXR400 are most often used during hours when researchers are in the building during the weekdays and weekends. Very few sessions last longer than 120 minutes. These spectrometers are used to perform short 1D experiments requiring a high degree of user interaction.

Utilization of the I400 and I500 is more uniform throughout the day and farther into the evening than the Gem300 and VXR400. Many sessions last longer than 120 minutes, especially on the I400 spectrometer. Longer experiments are performed with these spectrometers, which can run for substantial periods without user interaction.

The NMR Facility made substantial use of the I400, I500, and datastations, but no substantial use of the Gem300 and VXR400. These spectrometers and the datastations are used for non-routine experiments and non-routine processing. The NMR Facility Staff use the I400, I500, and datastations for development and performance of these types of experiments.

Utilization of the I400, I500, and datastations are very low during the weekends. These spectrometers are used for non-routine experiments and non-routine processing. These experiments require more assistance from the Staff (especially when probe changes are required to observe nuclei other than ¹H, ¹⁹F, ¹³C, and ³¹P), who are not typically available during the weekends.

Availability of datastation time is substantial, even during peak utilization periods during the day. The large majority of datastation sessions last less than 15 minutes. Datastations are very accessible; all three datastations are rarely in use for more than 15 minutes.

nmrsun1 is predominantly used for shorter sessions and nmrsun3 is predominantly used for longer

sessions. nmrsun1 has a slower processor, which is best suited for brief, routine processing. nmrsun3 has a faster processor, and is located nearer the Staff offices, which is best for computationally-intensive, Staff-assisted processing, such as linear prediction applied to two-dimensional experiments implemented by U. Werner-Zwanziger (see also About the Cover).

nmrsun1 utilization decreased and nmrsun3 utilization increased after July. This indicates a trend towards longer datastation utilization after July, which is partly attributed to non-routine data processing methods implemented by U. Werner-Zwanziger (see also About the Cover).

Inorganic chemists dominate utilization of the Gem300 and I400. Organic chemists dominate utilization of the VXR400. No research interest dominates utilization of the I500. Datastations 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 I500 by the Stone group increased I400 and Gem300 utilization by 7%, while VXR400 and datastation utilization remained relatively unchanged. Utilization of the I500 by the Stone group does not significantly impact upon availability of other spectrometers and datastations.

Notable services

A new record of 50 consecutive days without breaking a sample in the NMR Facility was established, which is the result of an informal program to increase safety awareness. The previous record was 31 consecutive days.

The NMR Facility Staff presented two lectures in C445 (Organic Spectroscopy) covering the basic procedures for one-dimensional and two-dimensional NMR experiments.

The Staff repaired and maintained the T60 NMR spectrometer in the undergraduate organic chemistry laboratories on three occasions.

Summary of Facility Developmentsi

Personnel

Dr. Ulrike (Ulli) Werner-Zwanziger joined the NMR Facility Staff on June 1, 1997. Ulli’s responsibilities as Manager of the NMR Facility include the design, performance, processing, & interpretation of non-routine NMR experiments and the design & repair of hardware required for non-routine experiments. This compliments Marty Pagel’s responsibilities as Director of the NMR & Molecular Visualization Facilities to form an extremely functional administrative model for the NMR Facility. Ulli also brings extensive experience with solid-state NMR spectroscopy to the Facility; as a consequence, a grant proposal to obtain a solid-state NMR spectrometer for the NMR Facility and departmental research is pending NSF approval.

Jeff Frey joined the NMR Facility Staff as the Operations Specialist on Oct 13, 1997, following positions with the Indiana Geological Survey and the IU Cyclotron Facility. Jeff’s responsibilities include training researchers, collaborating with researchers to perform NMR experiments, and maintaining & optimizing spectrometer performance. Jeff also brings substantial PC & UNIX computing experience and interests to the NMR Facility.

Ken DeHart, the NMR Facility Computing Systems Specialist, attended the Web Application Discussion Series and the Virtual Reality conference, both on the IUB campus. Ken also attended routine meetings of the UNIX Users Group, the Windows NT Users Group, the Association of Information Managers when his scheduled permitted and topics were appropriate. Ken’s responsibilities in the NMR Facility include installation, maintenance, and user support for the computers (7 Sun workstations, 3 Silicon Graphics workstations, and 4 PCs) as well as peripherals such as printers, plotters, and storage devices. In addition, Ken upgraded the Facility network to provide greater throughput and reliability. Ken’s proficiency with NMR spectroscopy techniques was especially helpful when the NMR Facility was temporarily understaffed.

Marty Pagel’s responsibilities as Director of the NMR Facility include advanced User training, software development, and administration. Marty’s notable developments during 1997 include new pulse sequences & processing programs, new additions to the NMR Facility web site, and collaborations with a variety of researchers.

Deon Osman transferred from the position of NMR Facility Electronics Specialist to the Research Computer Systems Group in the Department of Chemistry on June 1, 1997. Jackie Henley left the position of NMR Facility Operations Specialist on Sep. 5, 1997 to pursue a career in the pharmaceutical industry. We wish them both the best in their new positions and thank them for their contributions to the NMR Facility.

Spectrometer Improvements

The single-axis gradient module & gradient probe of the I500 NMR spectrometer was replaced with a triple-axis gradient module & gradient probe. This equipment increases the power and resolution of gradient effects required by the sophisticated NMR experiments needed for biochemical research.

A 10mm low-gamma Bradley probe was installed on the I400 NMR spectrometer, which allows researchers to perform experiments with exotic nuclei.

A 5mm FourNuc+ Nalorac probe was also installed on the I400 NMR spectrometer, which allows researchers to routinely perform ¹H, ¹⁹F, ¹³C, and ³¹P experiments without staff intervention, and novel binuclear and trinuclear experiments involving these four nuclei.

A FTS variable temperature unit was installed on the VXR400 NMR spectrometer for accurate, stable, low-maintenance temperature regulation.

An anti-vibration platform was installed beneath the magnet of the Gem300 NMR spectrometer.

Experiment Improvements

Binuclear and trinuclear experiments involving combinations of ¹H, ¹³C, ¹⁹F, and ³¹P were developed using the I400 FourNuc+ probe.

Phase-sensitive versions of many experiments were implemented to improve spectral resolution.

DEPT-Edited HETCOR experiments were implemented to distinguish methine, methylene, and methyl groups in standard HETCOR spectra.

Long-Range HETCOR experiments were implemented and optimized for identifying correlations between ¹H and ¹³C that are separated by two or three bonds.

HMQC experiments were implemented for smaller molecules.

16 MAGICAL II™ macros were developed for Varian-based NMR experiments and data processing.

Laboratory Improvements

A frequency synthesizer was purchased to facilitate probe tuning and spectrometer troubleshooting.

The NMR Facility electronics lab was reorganized and moved to room C239. The old electronics lab space was converted to office space.

The computer network was upgraded from a coax system to a 10-base-T switched network, for improved throughput and reliability.

The NMR Facility Web Site was migrated to a new URL (http://nmr.chem.indiana.edu). Additions to this web site include:

applications (Spectrometer Reservations, On-Line Roster, Experiment Counter)
information (IUNMR User’s Guide, Undergraduate Instruction, Suggestion Box)
public relations (Spectrum of the Month, Latest News, Publications & Reports)

Continuing Projects

The MAGnet REServation on-line scheduling system will replace the current paper-based system. Marketability of MAG RES and other NMR Facility web applications will be investigated.

A second waveform generator board for the I500 spectrometer has been purchased; this board will be installed and appropriate experiments will be implemented.

The acquisition of a solid-state NMR spectrometer is planned; a proposal has been submitted to NSF.

HSQC and Multiple Quantum experiments will be implemented for resolving crowded spectral regions.

1997 Graph Gallery

Data for the Graph Gallery was derived from NMR Facility accounting records from December 31, 1996 to November 30, 1997 (Dec 31, 1996 was included with Jan. 97). These records were automatically generated from the spectrometer & datastation login/logout processes; therefore, these records accurately reflect utilization of all spectrometers & datastations. All data is accurate to within 1 minute.

The Relative Utilization by Group pie charts show group utilization of each group relative to total time used. The "Others" category of these pie charts represent the sum of other groups, each of which had less than 5% utilization of the spectrometer or datastations. The Utilization of Total Time histograms show the utilization of each area of research interest when the Stone group was using the I500 spectrometer ("with Stone on I500" bar) or when the Stone group was not using the I500 spectrometer ("Without Stone on I500" bar).