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Reaction Monitoring Using NMR and Vibrational Spectroscopy – RSC Conference

March 7, 2011 by process nmr IR-ATR, NMR, PAT, Process NMR

Dr. John Edwards of Process NMR Associates will be attending an RSC sponsored one day symposium on “Reaction Monitoring Using NMR and Vibrational spectroscopy – An Industrial Perspective”. The meeting will be held at the Pfizer Research Center in Sandwich, Kent, UK on March 22, 2011. Dr Edwards will be presenting a poster entitled “Practical Applications of Compact High-Resolution 60 MHz Permanent Magnet NMR Systems for Reaction Monitoring and Online Process Control”. The abstract of the talk is presented below:

For the past two decades high resolution 1H NMR at 60 MHz has been utilized to monitor the chemical physical properties of refinery and petrochemical feed-streams and products. These approaches involve the use of partial least squares regression modeling to correlate NMR spectral variability with ASTM and other official test methods, allowing the NMR to predict results of physical property tests or GC analysis. The analysis is performed in a stop flow environment where solenoid valves are closed at the beginning of the NMR experiment. This approach allows up to 5 or 6 different sample streams to be sent to the sample in order to maximize the impact of the instrument. The current work with these permanent magnet NMR systems is to utilize them as chemistry detectors for bench-top reaction monitoring, mixing monitoring, dilution monitoring, or conversion monitoring. In the past use of NMR for these applications has been limited by the need to bring the “reaction” to the typical “superconducting” NMR lab. A compact high resolution NMR system will be described that can be situated on the bench-top or in the fume hood to be used as a continuous or stop-flow detector and/or an “in-situ” reaction monitoring system. The system uses a unique 1.5 Tesla permanent magnet with a simple flow cell and total system volumes of 2 to 5 ml depending on the length and diameter of the transfer tubing. Further, detection limits of analytes in the 200+ ppm range are possible without the use of typical deuterated NMR solvents. Analysis times of 5 to 20 seconds are also possible at flow rates of 5 to 20+ ml/minute. Reaction monitoring directly in standard 5 mm NMR tubes again using conventional (non-deuterated) reactants, solvents and analytes will also be described.

Details of the symposium and registration information can be found at the RSC website.

Benchtop Permanent Magnet High Resolution NMR Systems

November 24, 2010 by process nmr NMR, Process NMR

The latest buzz in the NMR news release world has been the emergence of the 45 MHz picoSpin (www.picospin.com) miniature NMR system that boasts shoe box size dimensions, a resolution of 80 ppb (3.5 Hz at peak half height), and a tiny 300 micron probe dimension. The sample can be injected with a syringe or pump. A number of application examples and spectra are posted on the application pages of the company website. It is noted that the spectra require the signal averaging of 24-200 pulses requiring an estimated experimental time of 3-10 minutes

The system claims to be the first miniature NMR system but I guess that depends on how you define “miniature”. A number of “relatively small” high resolution permanent magnet NMR systems operating at 60 MHz have been around since the early ’90s (Elbit-ATI, FoxboroNMR, Qualion, ASPeCT-MR, and ACT). The picoSpin NMR is definitely the first spectrometer to deliver high resolution NMR from such a small footprint permanent magnet combined with a capillary probe. The S/N of the picoSpin system is approximately 300:1 on a one pulse spectrum of water. On our 60 MHz systems we are routinely obtaining, non-spinning, one pulse spectra without signal apodization with a S/N of 1600:1 for a 5 mm sample size, and 3600:1 for a 10 mm sample size. Very little degradation of spectrum quality is observed moving from 5-10 mm probe systems. The 5mm lineshape spec is typically LW(50%)=2 Hz (34 ppb), LW(10%)=6 Hz, LW(0.5%)=20 Hz. For the 10 mm probe the spec is typically LW(50%)=2.5 Hz (43 ppb), LW(10%)=13 Hz, LW(0.5%)=80 Hz. We have many example spectra posted on this blog and on our website.

The S/N obtained with 5mm and 10mm sample dimensions represent a 28 and 144 fold improvement of sensitivity compared to the S/N obtained on the picoSpin system. This is a vitally important difference between these two technologies. One yields a useful, repeatable spectrum at a high S/N level after every pulse (4-5 seconds between spectra) while the other requires 100x longer time frame to obtain the same result. In the realm of reaction monitoring this time difference is a huge factor as a reaction can be at completion in a few minutes but an NMR analyzer providing a spectrum every 5 seconds allows dozens of observations to be performed in a short 2 minute reaction. The larger sample dimension in the 60 MHz systems also has the advantage of allowing a much wider range of industrial sector samples to be analyzed with respect to sample viscosity, contamination levels, sample temperature, and “particulate content”.

The picoSpin spectrometer does have a wonderful and truly portable package and will find many applications in university general chemistry labs and in QA/QC of liquid products, but I am not sure that it will have the stability and high sensitivity to allow it’s use in real time process control and reaction monitoring where the samples are complex mixtures, at high temperature, often with particulates present. Also the small probe dimension will mean that the analysis of flowing samples will be extremely difficult because of the small sample volume being analyzed.

Process NMR Associates is currently investigating the possibility of reducing the foot print of their 60 MHz NMR system to a platform that would support a 5 mm sample dimension operating at 60-80 MHz. The magnet would be closer to 50 lbs in weight in this scenario, and with a small FPGA based spectrometer would be a powerful mobile NMR system. However, I do not have a feel for whether the NMR and broader analytical community will be willing to accept the idea of low priced NMR systems selling in the $20-70K range. The question remains….if you build it, will they come? I would be interested to hear any comments on the utility of NMR in the field based on permanent magnet technologies at NMR frequencies of 45-80 MHz. Please address any comments to John Edwards.

IFPAC Conference: Process NMR Associates and University of California, Davis to Present Process NMR and MRI Short Course Prior to Meeting

November 24, 2010 by process nmr NMR, PAT, Process NMR, TD-NMR Tagged: NMR, Process Analytical

Short Course on Process NMR and MRI to be presented at the IFPAC Meeting (http://www.ifpac.com/)
When: Monday, January17, 1:00pm to 5:00pm, and continues on Tuesday January 18, 8:00AM to 12 noon
Location: Baltimore Marriott Waterfront
Instructors: Michael J. McCarthy, Professor of Engineering, University of California, Davis, CA
Paul J. Giammatteo, Ph.D., Process NMR Associates LLC, Danbury, CT

The course is specifically designed and organized for industry professionals who want to add to their knowledge-base on magnetic resonance and process analytical technology. Topics include compositional analysis, rheological characterization, measurement of the state of mixing, visualizing transport and product stability as well as recent advances in process magnetic resonance sensors. This course will bring you up-to-date on the latest information concerning the applications and state-of-the art instrumentation for process magnetic resonance.
Outline:
* Introduction to Process NMR Magnetic resonance theory
– Time-domain, High resolution, Diffusion, Imaging
* Hardware
– Spectrometers, magnets, probes
* Coupling the sensor to the process
* Applications will include:
– Composition measurement
– Property measurement
– Rheology measurement
– Product structure
For Details contact Paul Giammatteo Tel: (203) 744-5905 or Michael McCarthy Tel: (530) 752 8921

Process NMR Spectroscopy Chapter to Appear in Wiley Publication

March 22, 2010 by process nmr NMR, PAT, Process NMR, TD-NMR

John Edwards and Paul Giammatteo of Process NMR Associates have written a chapter “Process NMR Spectroscopy: Technology and On-Line Applications” to appear in the 2nd Edition of “Process Analytical Technology” published by Wiley and Sons and Edited by Katherine Bakeev. The book will be published in May 2010 and is available for pre-order.

Process Analytical Technology - 2nd Ed. - Wiley

Process NMR Under Continuous Flow

March 22, 2010 by process nmr NMR, PAT, Process NMR

The use of an NMR as a simple flow detector for benchtop reaction monitoring, mixing monitoring, dilution monitoring, or conversion monitoring has been limited by the need to bring the

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