In July I will be presenting an invited talk: “A Self-Employed Application Chemists Odyssey in the World of Analytical Instrument Development The Viability of a $50K High Resolution NMR and $15K ESR Spectrometers”, at the University of South Dakota, Vermillion, SD. The date has yet to be set.

I will be presenting an invited talk in a session on reaction monitoring with NMR at SMASH 2010 in Portland Oregon, September 26-29 – my talk is entitled: “Simple and Continuous Flow Reaction Monitoring by High Resolution Bench-top Permanent Magnet 1H NMR at 60 MHz”, by John C. Edwards, Paul J. Giammatteo, at SMASH 2010, in Portland, Oregon. Other speakers in the session include Søren Balling Engelsen of the UNiversity of Copenhagen speaking on “New chemometric methods for alignment (icoshift), classification (ECVA) and information extraction of NMR data”, and Encarnación Fernández Valle & Dolores Molero of the Universidad Complutense de Madrid – Fast 2D Methods for reaction monitoring of organic reactions.

Finally, I will present an invited talk entitled in a session on, “Bench-top and On-line High Resolution Permanent Magnet 60 MHz NMR for Reaction Monitoring and Process Control” , by John C. Edwards, Paul J. Giammatteo, in a session on Portable NMR and Hyphenation of NMR to Chromatography and Electrophoresis at FACSS 2010, in Raleigh, NC, October 17-21.

I’m available to discuss the NMR details of these presentations at any time – I will provide copies of the talks upon request. JE

1) SpinWorks – written by Kirk Marat at the University of Manitoba – Download Here

2) GSim – written by Vadim Zorin Download Here

3) RNMR (Requires R Statistical Freeware Package) – Download Here – R Software can be obtained here

4) MatNMR (Requires MATLAB) – Download Here

5) Hires – Download Here

One of the best journal articles on the topic is by Kazuyuki Takeda “OPENCORE NMR: Open-source core modules for implementing an integrated FPGA-based NMR spectrometer”, Journal of Magnetic Resonance, 192(2), 218-229, 2008. This gentleman also included all the core modules, console software, pulse programs and board designs required to build your own spectrometer (see Opencore Website). The availability of superconducting NMR magnets are still the barrier to entry for cheaper high field NMR systems but in the lower field NMR area these spectrometers will enable a drastic reduction in instrumentation cost and perhaps lead to a larger NMR market. In the near future I feel that NMR systems in the 200/300 MHz range will be quite affordable especially if the consoles are married to older magnets that are currently gathering dust in rear storage areas.

The appearance of Bruker’s Fourier 300 NMR spectrometer bears witness to the market that is there for a company that can deliver a well priced NMR instrument in combination with strong application software. In fact I think that these cheaper spectrometers will facilitate the development of a market where NMR instrumentation will be sold to address individual analytical problems in routine testing laboratories. Perhaps NMR standard methods will become as prevalent as GC and MS methods currently are. Imagine an NMR spectrometer sold to a laboratory not as a general research tool but as a dedicated instrument performing authentification testing on olive oils sold in the EU. This is a new concept for NMR chemists to wrap their heads around….smaller, cheaper NMR instruments driven by applications rather than magnetic field strength.

A two FPGA spectrometer design is illustrated in the two figures.

As an example, we observed the Hydrogen bonding exchange rate between the OH protons on isopropyl alcohol with the hydrogen of water as a function of increasing water concentration. Figure 1 shows the starting spectrum (blue) of “of the shelf” 91 vol % IPA obtained at the local pharmacy flowing through the NMR at 10 ml/min. At this concentration, the IPA OH hydrogen and water hydrogen are spectrally distinct. The red spectrum is the final spectrum after 50 minutes of slowing adding water to the original IPA to bring the IPA concentration to approximately 76 vol %. At the end of the dilution, the OH peaks from IPA and water are in complete exchange as represented by the single peak.

Figure 1: “Off the Shelf” Isopropyl Alcohol at the original concentration of 91 vol % IPA (blue) and diluted to 76 vol % (red).

Figure 2 shows the results of the sequential addition of 20 0.5 ml aliquots of water that take the original 91% IPA to its final concentration of 76%. As shown in Figure 3, one can readily observe the convergence of the OH peaks as the dilution progresses.

Figure 2. Continuous flow NMR dilution monitoring of 91% by volume isopropyl alcohol with water to a final concentration of 76%.

Figure 3. Continuous flow NMR monitoring of OH hydrogen exchange between water and isopropyl alcohol as a function of IPA concentration.

Continuous Flow NMR was also used to monitor solute addition in a non-mixed vessel. In this experiment a concentrated table sugar solution (2.19 molar) was injected every 100 seconds at an injection volume of 0.083 ml each for the first 30 minutes (1 ml total) with two final injections of 0.5 ml each. Starting volume of water was 25 ml. Total volume of sugar solution injected was 2.0 ml representing 1.5 grams of table sugar. Flow rate through the NMR flow cell was 10 ml/min with a total NMR sample volume (tubing + flow cell) was 5 ml. Again, no solvent suppression was applied.

Figure 4 shows the overall spectra through the entire run. Figure 5 shows the expansion of the water/carbohydrate region showing the sensitivity of the 60 MHz flow NMR to sugar concentration.

Figure 4. Overall flow NMR results for concentrated sugar solution addition to water.

Figure 5. Water/carbohydrate region expansion showing table sugar addition to water.

Reaction #1: Acetic Anhydride in Water – Reacts to form Acetic Acid

NMR Monitored Reaction Profile

Reaction #2: Acetic Anhydride + Excess of Methanol + Acid – Yields Acetic Acid and Acetic Methyl Ester

First Reaction was Performed without Shaking the Sample before Observation

NMR Monitored Reaction Profile

Second Reaction was Performed with a vigorous shake of the NMR tube before observation.

NMR Monitored Reaction Profile

For More Information Contact John Edwards

“Spectroscopy Based Crude Assays for Laboratory, At-Line, and On-Line Applications”

This Presentation can be found at the Crude Oil Quality Group Website (http://www.coqa-inc.org/061809Giammatteo.pdf)

A Self-Employed Application Chemists Odyssey in the World of Analytical Instrument Development The Viability of a $50K High Resolution NMR and $15K ESR Spectrometers

By John C. Edwards, Ph.D.
Process NMR Associates, LLC, Danbury CT

The availability of cheap commodity electronics developed for the cellular phone industry is revolutionizing the design of NMR and ESR spectrometers. Rather than instruments that fill half a room, cost $200-3,000K+, and intimidate users, it is possible to produce spectrometers that are an order of magnitude cheaper to produce. Examples of NMR and ESR spectrometer development projects will be described as well as the wide-ranging applications that these spectrometers can deliver to the areas or process control, food authentification and automated laboratory analysis.

John Edwards was born and raised in Bolton, UK. He graduated from the University of Durham, UK with a B.Sc. in Chemistry in 1986. He obtained his Ph.D. in Physical Chemistry from the University of South Carolina in 1990, working on solid-state NMR applied to heterogeneous catalysts under the guidance of Professor Paul Ellis. From 1990-1997 he worked as a research chemist at the Texaco R&D facilityin Beacon, NY where he was responsible for global NMR support of upstream, downstream, and petrochemical Texaco ventures. In 1997 he formed Process NMR Associates which operates as a commercial analytical NMR spectroscopy service and consultancy. Process NMR Associates along with its engineering company partners, develops, markets, and supports on-line process NMR spectrometers utilized for control and optimization of refinery, petrochemical, pharmaceutical and food manufacturing operations. The company also acts as an application development company for several analytical instrument companies and supports the chemometric development of several process analytical products. He currently resides in Poughkeepsie, NY, with his wife and 3 sons. He is an affiliate professor of Chemistry at Marist College, a Research Associate at SUNY New Paltz, and an active member of the American Chemical Society.

A copy of the presentation can be provided on request… contact John Edwards if interested.