State University of New York
College of Environmental Science and Forestry (SUNY-ESF)
Syracuse, NY, 13210
Alumni Lounge– Marshall Hall
October 12, 2007

Co-Organizers

Sponsors

• SUNY-ESF
• Syracuse University
• Bruker Biospin
• Bristol-Myers Squibb
• Process NMR Associates LLC
• Isotec
• Cambridge Isotope Laboratories
• Varian Inc.

The 9th annual Upstate NY NMR Symposium will be held at SUNY-ESF on Friday, October 12th featuring keynote speaker Professor Ruth E. Stark, Director Institute for Macromolecular Assemblies, CUNY. Others from around the region will also highlight their work in short presentations and posters.

• Tentative oral presentation program
• Poster session program (posted by 9/12)

There is no cost to attend this symposium due to the generosity of the sponsors listed above but pre-registration is required

• Registration form

Lodging arrangements have not been made for this symposium but a variety of options are available:

• Lodging Options

The conference will be held in the Alumni Lounge (a.k.a. Nifkin Lounge), Marshall Hall on the SUNY-ESF campus located adjacent to Syracuse University.

• Maps and Directions

Parking has been arranged in the Irving Garage just a short walk from Marshall Hall (campus map).

Tentative Program

Eastern Analytical Symposium – November 12-15, 2007
Garden State Convention Center, Somerset, New Jersey

Process NMR Technology Sessions
Wednesday, November 14, 2007
Chair: John Edwards, Process NMR Associates
Sponsored by Process NMR Associates

Process NMR Technology I: High-Resolution Studies

9:00 “Introduction to NMR in Process Control”
John Edwards, Process NMR Associates

9:25 “Standardizing and Stabilizing NMR Calibration Transfer”
Miko DeLevy, Qualion NMR Analyzers

9:50 “More from the Barrel – On-line NMR Increases Diesel Production and Quality”
Paul Giammatteo, Process NMR Associates

10:15 Break

10:35 “Taking NMR into the Refining Process: Best Practices and Benefits”
Marcus Trygstad, Invensys Process Systems

11:00 “Get Your Head Out of the Sand: Use of Reaction NMR to Better Understand Reactions in Process Development”
Andreas Kaerner, Eli Lilly

11:25 “Direct Prediction of Gasoline Properties for Monitoring Refinery Processes by H-1 NMR Spectroscopy”
Veena Bansal, Indian Oil Company

Process NMR Technology II: Time-Domain Studies
Chair: John Edwards, Process NMR Associates
Sponsored by Process NMR Associates

2:00 “Recent Developments in Time-domain NMR and Its Applications in Polymer Industry”
Harry Xie, Bruker Optics

2:25 “Time-domain NMR: Uses and Contributions to Process Control”
Vaughn Davis, Progression

2:50 “Recent Progress of NMR and MRI in Petroleum Exploration”
YiQiao Song, Schlumberger-Doll

3:15 Break

3:35 “Applications of Time-domain NMR to Laboratory and On-line Polymer Analysis”
Maziar Sardashti,ConocoPhillips

4:00 “Challenges in On-line Water Cut Monitoring of Heavy Oil Thermal Operations Using Low Field NMR”
Sergey Kryuchkov, University of Calgary

4:25 “Benchtop Fluoride NMR: A Rapid QC/QA Method”
Chris Borgia, Colgate-Palmolive

The Mid-Hudson Section of the American Chemical Society and Vassar College Announce

“The Wood-Based Biorefinery in a Petroleum Depleted World”

Dr. Arthur J. Stipanovic,

Professor and Chair, Department of Chemistry

State University of New York, College of Environmental Science and Forestry (SUNY-ESF)

Wednesday, November 7th, 2007

Time: 7:00 pm

Location: Mudd Chemistry Building, Third Floor

Refreshments will be served at 6:30 pm

Vassar College, Poughkeepsie, New York

Contact: Dr Joseph Tanski (jotanski@vassar.edu, 845-437-7503)

Abstract: The 21^st century is envisioned to become the “age of biology” as renewable biomass resources replace petroleum in energy and industrial product applications. Motivated by concerns over national energy security, global CO₂ reduction, a need for biodegradable products, and enhanced rural economic development, the engineering and construction of “biorefineries” for the manufacture of fuels, chemicals, polymeric materials and power from renewable resources is now a critical national priority. The context and intent of a biorefinery must be much more than simply replacing crude oil with renewable raw materials. A successful biorefinery must: 1) efficiently separate its raw material source into individual components, and, 2) be able to convert these components into marketplace products. The biorefinery must mirror the efficiency of today’s modern petrochemical refinery in using all components of its raw material source for the production of chemicals, fuels, and power.

Woody “lignocellulosic” biomass is a complex, composite material consisting of three polymers in close association: hemicellulose, cellulose, and lignin plus small amounts of low molecular weight extractives and inorganics. In this presentation, a group of synergistic biomass feedstock and “biorefining” technologies under development at SUNY-ESF, in collaboration with many industrial and academic partners, will be discussed including: short-rotation fast growing willow production, biodelignification, hemicellulose extraction, polymer conversion to fermentable sugars, biodegradable thermoplastics and hemicellulose-based composites.

See the Stipanovic Website at SUNY_ESF for further details…..http://www.esf.edu/chemistry/faculty/stipanov.htm

Bio: Dr. Arthur J. Stipanovic is currently Professor and Chair of the Department of Chemistry at the SUNY College of Environmental Science and Forestry (SUNY-ESF) in Syracuse , NY , and also serves as Director, Analytical and Technical Services. His research interests include biodegradable polymers from renewable resources, high-throughput analytical techniques for determining the composition of woody biomass and new processes for the wood-based biorefinery. Dr. Stipanovic received both his B.S. and Ph.D. degrees from SUNY-ESF in polymer chemistry and much of his career was spent at the Texaco R&D labs in Beacon, NY, in new technology and lubricants research. He is a past Councilor and Executive Board member of the Mid-Hudson ACS section and, more recently, has served as Chair of the Syracuse section.

Directions: Vassar College is located off Raymond Avenue in Poughkeepsie , NY. Refer to the following link for driving directions and campus map: http://www.vassar.edu/directions/. Enter the Main Entrance of the campus on Raymond Avenue and go right towards the Mudd Chemistry Building. The Security Guard at the Main Entrance will direct you to parking.

NMR analysis of Jasmine Absolute.

For more information on NMR of Essential Oils visit the PNA website.

Fish Oils - Flaxseed Oils

NMR is extensively utilized to analyze fish oils and edible oils high in omega-3 fatty acids.

Examples of ¹H and ¹³C data and analysis are provided below:

¹³C NMR Analysis of Fish Oil Supplement

¹³C NMR of Flaxseed Oil Supplement

Brief Overview of Wine Analysis by ¹H and ¹³C NMR

Wine analysis by ¹H or ¹³C NMR can be used to follow acid content during maturation. Lactic, succininc and acetic acid can be followed readily by both techniques and presence of sugar, glycerol, and methanol can be observed.

Chemometric approaches are starting bear fruit with respect to quantitative analysis:

¹H and ¹³C NMR NMR is typically obtained using deuterated NMR solvents to lock the field during acquisition. In some cases the use of these solvents is problematic as it prevents observation of solublized phases present in the sample. As an example we show here the NMR data obtained on a biodiesel production process. One of the major issues with the FAME product is the presence of glycerol in the product. NMR analysis is usually performed by dissolving the FAME in CDCl₃ in which glycerol is completely insoluble. Thus NMR analysis performed in this way does not allow analysis of residual glycerol content. However, if the FAME is run neat this issue does not arise.
Another analysis of enormous interest from the process control standpoint is the analysis of the glycerol/methanol phase. This phase contains considerable free fatty acids as well as the glycerol by product and excess methanol from the transesterification process. The three components are readily observed by ¹H and ¹³C NMR, and ²³Na can be used to observe NaOH content in the phase. Finally the shift and shape of the observed OH resonance can yield information on the pH of the glycerol phase. Typically this analysis is done in DMSO-d₆

Below are some examples of NMR obtained without a deuterated solvent:

Difference in aliphatic carbon distribution between FAME phase and Free Fatty Acids (FFA)

found in the glycerol - methanol phase.

1H NMR of aliphatic component found in the FAME phase as well as the FFA in the glycerol phase.

I am posting this on behalf of Damien Jeannerat.

PhD Position Available Starting in September 2007

The 19.5 MHz Spintrack NMR analyzer was utilized to study a FAME biodiesel production reaction. The samples analyzed were: 

1) Used vegetable oil

2) Partially transesterified biodiesel product (bad biodiesel) 

3) High yield FAME biodiesel product 

4) Glycerin by-product from the process

CPMG T2 decays were generated and then that data was processed with a inverse laplace transformation to produce T2 distribution profiles.

NMR Experiment explanation is given below:

The CPMG data obtained on the four samples is shown below:

The T2 distribution profiles obtained by inverse Laplace transformation of the CPMG data are shown below:

Plainly TD-NMR can play a role in monitoring the biodiesel production process.

The 19.5 MHz Spintrack NMR analyzer was utilized to study a large series of  vacuum gas oils and FCC feeds for which PNA also has laboratory test data.

The analysis was performed on a SpinTrack 19.5 MHz TD-NMR spectrometer - CPMG T2 decays were generated and then that data was processed with a inverse laplace transformation to produce T2 distribution profiles. These T2 distribution profiles are currently being correlated to physical and chemical property data.

NMR Experiment explanation is given below:

The CPMG data obtained on the four samples is shown below:

The T2 distribution profiles obtained by inverse Laplace transformation of the CPMG data are shown below:

The correlation between T2 distribution and the metal content, viscosity, distillation range, density, asphaltene content are all being investigated at the current time.

pdf version

Below are examples of ¹³C NMR data obtained on biodiesel (FAME) and the vegetable oil precursor that it was made from by transesterification process involving microwave activation of the reaction between triglycerides and methanol in the presence of a caustic catalyst. Process NMR Associates is developing correlations between ¹³C NMR data and biodiesel properties stipulated in ASTM 6751.

Today one often finds hydrocarbon mixtures described by the detailed carbon type analysis that is possible from ¹³C NMR.

Many petroleum related products are being described in this way in patents leading to a novel way of describing a material and restricting others from using those same materials in products of their own. See Exxon, Mobil, and Chevron patents such as:

 6,090,989 ;  6,210,559  ;  6,059,955  ;  6,846,778  ;  20050077208  ; and 20050077209

In this PDF file we have shown some of the details present in a ¹³C NMR spectrum on petroleum products such a base oils, gas oils, diesels, etc.

Details of NMR Analysis

There are some issues with the assignements of many of these patents … for more details on how NMR might be of use in the patent process contact John Edwards

pdf version

PDF Version

¹H NMR has been used extensively by Process NMR Associates to determine PIONA analysis of Naphthas and to determine detailed aromatics breakdown in aromatics unit feeds, products, and intermediate products. Below are a few examples of naphtha chemistries that are observed and quantified by ¹H NMR.

Conjugated Olefin analysis is performed by a combination of HH-COSY and 1D ¹H NMR.

For more details contact John Edwards

Saudi Aramco Research and Development are searching for an experienced NMR spectroscopist - see details

Anyone who has NMR employment opportunities should contact Process NMR Associates. We would be happy to post you job listing to our blog and website.

If interested please e-mail a job description, requirements, and contact information to John Edwards

 PDF Version

Three samples were analyzed to determine if liquid or solid-state NMR techniques could be utilized to quantify adulteration of licorice powders by maltodextrin. Samples analyzed were:

Maltodextrin, Licorice #1, Licorice #2

Licorice #1 and Licorice #2 were analyzed by a combination of liquid-state ¹H and ¹³C NMR on a Varian Unity-300 spectrometer, and solid-state ¹³C NMR on a Varian UnityPlus 200 spectrometer. The resulting spectra are shown in the attached plots.

One of the Licorice samples is adulterated by maltodextrin to an unknown concentration, the other licorice sample is pure licorice. Which sample was which was not known during the analysis. Initially it was hoped that the addition of maltodextrin to the licorice would be readily observed as new peaks appearing in the spectrum of the licorice sample. However, it can be seen that in both the ¹H and ¹³C NMR there is considerable overlap of the peaks in the spectra of pure licorice and maltodextrin.

When no observable maltodextrin peaks could be assigned it was decided to simply use the quantitative integral data from the regions of the spectrum where the maltodextrin overlaps with the licorice spectrum compared to the integrals obtained from regions solely assignable to licorice. In Tables 1-3 are the quantitative results for each of the experiments performed.

Table 1: ¹H NMR Integral Regions

Regions 1 and 2 contain maltodextrin/licorice peaks.

Regions 3 and 4 contain only licorice peaks …. Data was norma lized to region 4. The norma lization norma lizes the licorice signal intensity. Thus the increased intensity of regions 1 and 2 in sample #1 is indicative that this sample contains maltodextrin. Samples #1+ and #2+ were made by adding more maltodextrin to the samples. Sample #1+ contains a further 10.9 wt % maltodextrin, while sample #2+ contains 11.4 wt% maltodextrin. The values were used to calculate the maltodextrin content in sample #1.

The ¹H analysis indicates that there is 3.3 wt% maltodextrin in sample #1

Table 2: ¹³C NMR Integral Regions

Regions 1-3 were common to licorice and maltodextrin signals, while regions 4-7 were exclusive to licorice signals. Normalization on region 7 sets the licorice at a norma lized intensity. Again the intensty of regions 1-3 increases from sample #2 to sample #1 indicating the presence of maltodextrin in sample #1.

Calculation indicates that there  is 6.1 wt% maltodextrin in the sample.

Table 3: Solid-State ¹³C Integral Regions

Region 1 contains maltodextrin and licorice signals, while regions 2 and 3 contain only licorice signals.

Again, the intensity of region 1 increases from sample #2 to 31 upon norma lization of the licorice only region 3. This confirms the presence of maltodextrin in sample #1. Samples #2+ and #1+ were not analyzed by solid-state NMR. This ¹³C analysis is much faster than the liquid-state NMR and would be a plausible short cut to quantify maltodextrin content.

  Upon completion of the analysis it was revealed that the adulteration value was 5% maltodextrin.

PDF Version - AppNote - Spectra

John Edwards of Process NMR Associates has organized and sponsored two symposium sessions at the Eastern Analytical Symposium in Somerset New Jersey, November 12-15, 2007. One session will focus on high-resolution process NMR and the other on applications of TD-NMR in process control. The speakers and talk titles are listed below. Check the EAS site for exact details on the date and time of the sessions (EAS website). If you are interested in attending and would like to submit a paper for presentation visit the EAS Abstract submission site.

Session Title: Process NMR Technology - High Resolution NMR

John Edwards, Process NMR Associates, “Introduction to NMR in Process Control”

Miko DeLevy, Qualion NMR Analyzers, “Standardizing and Stabilizing NMR Calibration Transfer”

Paul Giammatteo, NMR Process Systems, “More from the Barrel - On-line NMR Increases Diesel Production and Quality”

Marcus Trygstad, Invensys Process Systems, “Taking NMR into the Refining Process:  Best Practices and Benefits”

Andreas Kaerner , Eli Lilly, “Get Your Head Out of the Sand: Use of Reaction-NMR to Better Understand Reactions in Process Development”

Veena Bansal, Indian Oil Corporation, “Direct Prediction of Gasoline Properties for Monitoring Refinery Processes by 1H NMR Spectroscopy”

Session Title: Process NMR Technology - TD-NMR

Harry Xie, Bruker Optics, “Recent Developments in Time-domain NMR and its Applications in Polymer Industry”

Vaughn Davis, Progression Inc, “Time Domain NMR: Uses and Contributions to Process Control”

YiQiao Song, Schlumberger-Doll, “Recent Progress of NMR and MRI in Petroleum Exploration”

Maziar Sardashti, ConocoPhillips, “Applications of TD NMR to Laboratory and On-line Polymer Analysis”

Sergey Kryuchkov, University of Calgary, “Challenges in Online Water Cut Monitoring of Heavy Oil Thermal Operations Using Low Field NMR”

Chris Borgia, Colgate Palmolive, “Benchtop Fluoride NMR:  A Rapid QC/QA Method”

A series of Trans Fat standards was purchased from AOCS. The ability of ¹H and ¹³C NMR to predict Trans Fat Content as well as 

Saturated, Poly-unsaturated, and Mono-unsaturated Fat Content

The data of the samples is presented in the table below:

PLS regression techniques were used to correlate ¹H and ¹³C NMR spectral variation to the unsaturation level and type of unsaturation of the samples.

Processed ¹³C data is shown below:

¹H NMR data is shown below:

The following correlations were obtained from the ¹³C NMR data.

The data below shows the ability of ¹³C NMR to assign the natural product distribution found in essential oils. Once assignment of the oil hgas been obtained by ¹³C NMR the ¹H NMR can also be assigned. For QA/QC a benchtop 60 MHz system has enough resolution that authenticity of essential oils can be performed either visually of by PCA type analysis.

Ger - Geraniol         GerAc - Geranyl Acetate        iEugMe - Methylisoeugenol       Bor - Borneol

aPin - alpha-pinene        Lim -  Limonene        tOci - trans-beta-Ocimene      Cen - Camphene

Cllo - Citronellol        Clla - Citronellal        GenD - Germacrene D         aCal - Citral A (Geranial)

aTol - alpha-Terpiniol         cOci - cis-beta-Ocimene        Myr - Myrcene

¹H NMR has been used extensively to analyze biodiesel the vegetable oil feeds, reaction intermediates, and final products of the biodiesel transesterification process.

See Oliviera et al, Talanta 69 (2006) 1278-1284 and Gnothe, J. Am. Oil Chem. Soc 78, 1025-1028 (2001)

The final biodiesel product is a B5 (5% Biodiesel) or B20 (20% Biodiesel) blend of biodiesel in refinery produced diesel fuel. Researchers have performed method developments to analyze the biodiesel content in diesel fuels by NIR using 1H NMR as the primary method to quantify the biodiesel content. (See Jin et al, Fuel 86(7-8), 1201-1207 (2007) and Knothe J. Am. Oil Chem. Soc. 77 489-493 (2001). Process NMR at 60 MHz can be used to quantify the biodiesel directly. Below is an example slide of a biodiesel 1H NMR spectrum compared to two different diesel fuel spectra.

The chemistry that is directly observed in the NMR spectrum as well as the distinct chemical regions that are present in the diesel and biodiesel make this analysis relatively straightforward. Chemometrics can be used or quantitation can be obtained directly from a simple spectral calibration.

Biodiesel Production Monitoring

NMR can be used to follow the reaction of biodiesel directly, the following slides show the steps in the transesterification process.

Glycerol content in the biodiesel or unconverted vegetable oil content can be determined easily directly from the spectrum.

Expansion of Incomplete Reaction Series

Work is currently underway to develop NMR calibration models that can predict the various quality parameters specified in ASTM D6751 for biodiesel.

These calibrations, based on either ¹H or ¹³C NMR, when validated would allow rapid testing of biodiesel production batches and would make complete analysis of small production batches economically feasible (there is no point making 300 gallons of biodiesel if you have to perform $1300 of testing on the batch).

Press Release - NMR Process Systems - Danbury CT - February 14, 2007  

John Edwards of Process NMR Associates has agreed to chair a session at the Eastern Analytical Symposium in Somerset, New Jersey in November, 2007. The session is entitled “Process NMR Spectroscopy”. If you are interested in presenting a technical paper at this session please contact John directly at john@process-nmr.com

Also listed here is the 2007 Call for Papers for the upcoming meeting.

Dr Edwards of Process NMR Associates recently joined the American Chemical Society (ACS) speaker service which provides a clearing house for speakers who lecture on chemistry topics at local ACS Section Meetings that are typically held once a month during the academic year. Dr Edwards’ talk abstract and bio are provided below. Feel free to contact Dr Edwards if you are interested in hosting his talk at your meeting.

Biographical Sketch

Dr. John C. Edwards

Dr Edwards is currently a partner in Process NMR Associates, LLC where he is responsible for commercial analytical NMR services as well as development of on-line and at-line applications of NMR technology. He received his B.Sc. in Chemistry from Durham University in the UK (1986), and then received his Ph.D. in Physical Chemistry from the University of South Carolina in 1990. His doctoral studies involved solid-state NMR of catalyst materials. He was responsible for all NMR services with Texaco Inc from 1990-97 where he developed his particular expertise in petroleum and petrochemical NMR. In 1997 began Process NMR Associates which is involved in application of high resolution NMR spectroscopy for on-line process control as well as providing commercial analytical NMR service to over 250 industrial and academic customers around the world. Over the past 20 years Dr Edwards has developed an expertise in many types of non-traditional NMR equipment and applications.

Contact : John Edwards, (203) 744-5905 E-Mail: john@process-nmr.com

Press Release - NMR Process Systems - Danbury CT - January 19, 2007

As part of its announced multi-million dollar refinery improvement prog ram , Big West of California, LLC has selected NMR Process Systems LLC (NPS) to provide on-line NMR technology. The NPS integrated sampling and NMR analyzer system will enable the refinery to both increase its diesel production, as well as achieve quality targets needed for the new Clean Fuels Flying J will produce at it’s Bakersfield, CA, refinery. NPS’s NMR technology solutions, coupled with a Swagelok® sampling system, will perform simultaneous, multi-property diesel measurements required for process monitoring and control in the manufacturing of these new fuels. Installation is scheduled for the first quarter of 2007.

NMR Process Systems LLC, of Danbury, Connecticut (www.nmr-automation.com) is a process analytical technology and engineering services company, providing process analytical solutions to maximize plant and manufacturing operations in the refining, petrochemical, pharmaceutical and food industries. Solon, Ohio based Swagelok Company (www.swagelok.com) designs, manufactures, and delivers an expanding range of high-quality fluid system products and solutions.

Contact:
Paul J. Giammatteo
Product and Marketing Manager
NMR Process Systems, LLC
87A Sand Pit Road
Danbury, Connecticut 06810
Tel: +1-203-744-5905
paul@nmr-automation.com
www.nmr-automation.com

Since October 2006 “Old Swan” has been posting an excellent blog on NMR software. It can be found at nmr-software.blogspot.com

It makes very interesting reading … though I’m not always sure what is going on - see the December 11th posting

A new website has been introduced that focusses on the applications of Magnetic Resonance (NMR, MRI, Relaxometry) to the chemistry and physics of foods. The website can be found at magres.foodsciences.org

This organization also arranges the biannual conference on Application of Magnetic Resonance in Food Science - they have an excellent poster session with PDF versions of the poster presentations published to the web - Poster PDFs

This excellent database can be downloaded from http://ars.usda.gov/Services/docs.htm?docid=10491

This is what the authors (Sally A. Ralph, John Ralph and Larry L. Landucci.) said about the database:

“This NMR database has been designed to aid plant cell wall chemists in general and lignin chemists in particular. By compiling data from a series of model compounds run under strict acquisition conditions in three solvents, we hope to provide a compilation useful for cell wall NMR research.”

International Humic Substances Society – details on standard humic and fulvic acid isolation methods – standard materials – NMR reference data on standard materials.

A few society websites to keep an eye out for meetings as well as a few meeting links that I have come across recently.

International Society for Magnetic Resonance in Medicine

Clinical Magnetic Resonance Society

European Society for Magnetic Resonance in Medicine and Biology

Japanese Society for Magnetic Resonance in Medicine

Society for Cardiovascular Magnetic Resonance

Magnetic Resonance Managers Society

RSC NMR Discussion Group

Finnish NMR Discussion Group

Spanish Magnetic Resonance Society

Austrian NMR Discussion Group

Australian and New Zealand Society for Magnetic Resonance

German Magnetic Resonance Discussion Group

Italian Magnetic Resonance Discussion Group 

49th Rocky Mountain Conference on Analytical Chemistry – July 22-26, 2007 – Beaver Run Resort, Breckenridge, Colorado 

A very useful NMR frequency/receptivity map from Alexej Jerschow at New York University – Interactive Map and Table

An excellent view on the latest new technologies appearing on the scene of mobile magnetic resonance. Though the review is fairly thorough in the “new technologies”, it does not mention the mobile permanent magnet based spectrometers currently availbale from Process NMR Associates. I don’t know why traditional mobile NMR instrumentation is repeatedly ignored in this arena. The perception is out there that NMR will always be expensive to buy, maintain and operate. The truth of the matter is that high-resolution NMR instrumentation should cost less than $100K and low field relaxometers should cost below $30K. Automation is possible for all aspects of NMR operation from locking, shimming, pulse sequence calibration, gain settings, and post processing procedures. I’d love to hear comment from people on this as I’ve been scratching my head for years as to why people aren’t interested in low field spectrometers anymore for undergraduate and industrial applications.

Yet another masterpiece from tenderbutton – NMR of earwax.

The EUROMAR 2007 magnetic resonance conference will be held in Tarragona, Spain, July 1-6 at the Tarragona Trade-Fair and Congress Centre. Satellite meetings will be held on July 6.

The Canadian Association of Petroleum Producers has produced a test method to quantify olefins in crude oils, condenates and diluents. The method is particularly aimed at heavy oils and bitumens and their products that are not amenable to traditional olefin analysis. The method is published at the following link. We have developed many methods similar to this and have the ability to quantify and speciate the olefins present in the sample. The current CAPP method developed by the Canadian Crude Quality Technical Association (CCQTP) can be used to obtain total olefin content. Further NMR analysis and a few other experiments would allow some more detailed olefin chemistry distributions to be determined as well as observe the presence of conjugated diolefins that would be particularly troublesome in the processing of these materials. 1H NMR spectroscopy can be used very effectively to obtain many chemical and physical properties of crudes, heavy crudes, bitumen, and the distillate products that are produced by these materials. 1H NMR spectral correlation with these properties by PLS or non-linear PLS regression can yield extremely robust models, and for the chemical properties much more detailed chemical structure information can be obtained fro combining 13C NMR data with 1H NMR results.

CCQTP is an association with members that span multiple segments of the Canadian oil industry -it’s history, mission, and membership can be found at the site.

On a related note an excellent technical site dealing with crude oil quality issues cane be found at the Crude Oil Quality Group website, which is a consortium with the following membership, dedicated to developing test methods and quality standards for crude oil trading that go well beyond the traditional gravity and sulfur measurements currently used. There are many additives, processing fluids, corrosive materials that can be found in crude oils that can cause processing issues for the buyer who purchases simply based on density and sulfur. The group has made public much of it’s meeting agenda archives and the presentations given at those meetings. It is an interesting read for those interested in petroleum chemistry issues.

At PNA we have been developing some high field and low field NMR techniques, looking at chemistry and relaxation in crude oils with naphthenic acid and corrosion issues. We would be interested in hearing from anyone interested in woprking with us to develop a relatively straight forward method for NAN and TAN analysis by NMR methods. 

Found and interesting site touting quantitative NMR as a new concept….seems strange as 99% of the NMR work I have done is considered quantitative. There is a perception out there that 13C NMR is always qualitative. This has been confirmed to me in conversations with organic chemistry professors who will perform quantitative 1H NMR all day long and even justify higher magnetic field instruments based on lack of resolution in 1H data as they have the perception that 13C is purely qualitative and don’t think of the superior resolution and chemical shift information present in 13C spectra. The website is at qnmr.com, and contains an excellent petroleum chemistry example of the development of quantitative 13C NMR for aromaticity determination by Joe Ray, ex Amoco NMR researcher.

There is also an excellent link to a paper on the quantitative NMR of natural products.

There is an excellent overview of solid-state NMR at my alma mater Durham Univeristy in the UK. The page can be found at the following link.

Yesterday started typically, ran a few 1H NMR for some customers, developed a low-field NMR method for diesel and kerosene hydrogen content correlated to aromaticity, try to run some fibers for moisture and spin-finish. Suddenly 5:30 loomed, the Mrs called to ask when I’d home for dinner ….. so rather than incur the wrath of the spouse by continuing late with the work, I simply picked up my NMR and went home with it. The new SpinTrack 20 MHz system is essentially a desktop computer sized console with a 6×6x6 inch magnet weighing 14 lbs. The whole shabang runs off a USB connection to my laptop. Thus …. I spent today completing the work from the comfort of my home office … Beautiful ! Tomorrow I might just carry the system upstairs, put it on the coffe table and acquire some more data while watching the Tour de France on TV. Not many people can say they take their NMR machines home with them at night. This could become a regular thing for me.

Surfing the web I came across a surprising announcement … it appears that Progression Systems is interested in developing a 80 MHz high temperature superconductor electromagent system to utilize in their process NMR business. Does this mean that Progression will be entering the high resolution NMR domain or raising the resonance frequency and sensitivity of nuclei other than proton (27Al, 23Na, 31P, etc.)? Below is the news bulletin from Industrial Research Ltd (News Bulletin found at: http://www.irl.cri.nz/newsandevents/Mediareleases/joint-venture-for-hts110.aspx).

Joint venture for HTS-110

HTS-110 is a subsidiary company of Industrial Research Ltd – it’s HTS magnet technologies are described here.

The Abstracts for the Posters and Speaker Sessions of the 8th International Conference on The Application of Magnetic Resonance in Food Science (July 16-19, 2006) can be found at the following locations – Poster Abstracts and Speaker Abstracts .

Stelar s.r.l. has announced that it will be producing a new benchtop design for it’s Fast Field Cycling NMR product becoming available in September 2006, and also the availability of a new single board NMR console - available June 2006. the company has also formed a JV company called Invento s.r.l. which is a combination of Stelar and a business incubator at the Univerity of Torino. The mission of Invento is to further the development of FFC NMR techniques as standard methodolgies in testing laboratories and to perhaps replace other TD-NMR spectrometers.

A group of physicists at the University of Manchester are developing NMR probe technologies to monitor the magnetic field strength inside the solenoids of the Atlas LHC at CERN. The probe technology and accompanying NMR spectrometers are described on the Manchester website.

ENITechnologie will be presenting a paper on the on-line application of NMR in lube plant operation at the upcoming ACS Meeting in San Francisco

Experiencing Process MRA Industrial Lube Plant Application – Roberto Giardino¹, Silvia Guanziroli¹, Cinzia Passerini¹, and Antonio Farina². (1) EniTecnologie S.p.A, via Maritano, 26, San Donato M.se (MI), 20097, Italy, (2) Divisione Refining & Marketing – Raffineria di Livorno, Eni S.p.A, via Aurelia, 7, 57017 Stagno (LI), Italy

In a conventional base oil production plant the operating conditions needed to produce products at a desired specification are very sensitive to feed quality. At Livorno refinery an on-line Process Magnetic Resonance Analyzer (MRA) has been installed to identify the feedstock and product composition and properly set an advanced process control system. By using MRA it is possible to reduce the product quality give-away due to feed quality variation. In this work the industrial experience acquired is reported.

Characterization, On-Line Monitoring, and Sensing of Petroleums and Petrochemicals 8:30 AM-11:30 AM, Thursday, 14 September 2006 Sheraton Palace—Telegraph Hill

Division of Petroleum ChemistryThe 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006

Due to it’s broad versatility the Spin Track NMR Hardware supports all standard NMR routines such as AOCS Cd 16b-93, AOCS Cd 16-81, ISO 8292, IUPAC2.150 and creative scientific research. Spin Track has been successfully approved in the food and polymer industries for routine analysis. If your application is not described below please contact John Edwards for discussion. 

Solid Fat Content (SFC) Analysis
The quality of food products containing fats and oils depends on solid fat content (SFC). SFC determination is an essential measurement in the baking, confectionery, and fat industries. NMR has been established as the method for SFC determination by ISO 8292. Measurements of SFC by the Spin Track NMR analyzer can be performed quickly and accurately with great benefit for the manufacturer. 

Simultaneous Rapid-Determination of Oil and Water in Seeds
Sunflower, soybean, groundnut, rape and mustard are appreciated for their oil content, but excess of water content reduces their price. Thus, an accurate and fast determination of oil and water content is important to both manufacturers and customers. The Spin Track NMR analyzer meets ISO 10565 requirements and gives the possibility to simultaneously determine of oil and water content.

Oil/Fat and Moisture analysis in Chocolate, Powdered Milk, Cheese and other Food Products
Time of storage of food products depends strongly on moisture content. Excess moisture leads to microbiological activity and can make food consumption dangerous. Fat and moisture content also heavily  influence taste. Manufacturers are also regulated to disclose the exact information on the fat content of their products. NMR is the most rapid and exact method to determine these essential parameters. The Spin Track NMR analyzer is especially suitable for regular analysis of food quality. 

Curing Degree and Elasticity Analysis in Rubber-Type Materials

Over the past years Rheology has become widely accepted as a tool in the investigation of rubber properties. However, rheological testing equipment can  be extremely expensive and complicated. NMR is very sensitive to the structure and properties of investigated rubber materials. The Spin Track NMR-analyzer allows investigators to obtain data complementary to rheology and can also prove to be more informative. 

Moisture and Crystallinity Analysis in Polysaccharides
Polysaccharides like chitin, chitosan etc. are widely used because of inherent unique properties. Adsorbents and food bio-additions based on them require a regular check of quality. Spin Track NMR-analyzer allows investigators to obtain information about moisture, crystallinity, purity and structure of polysaccharides.

Porosity of Rock Cores/Heterogeneous Catalysts/Zeolites
The possibility of oil development can be defined more exactly in the initial stages of exploration by using NMR. Rock cores saturated by bitumen or water provide information on degree of saturation, structure of saturating compounds, porosity, and diffusion characteristics. This information allows the prediction of oil production yields. The Spin Track NMR-analyzer with a 35mm probe gives the possibility to obtain such information.

Scientific applications
The spectrometer’s Relax software allows construction of many types of NMR pulse sequences, user-defined interfaces, data processing (digital experiments filtering, fitting, Fourier and Laplace transforms) and data manipulations. Thus, customers can directly run automated standard type NMR experiments just by “pressing one button” in the program shell, or create new applications using the powerful pascal-like script language. Widely used experiments like measurements of T₁ and T₂ (90-tau-90, 180-tau-90, CPMG, FID, Spin Echo, Solid-Echo) are included into the Relax software as default examples. The NMR measurements can be accompanied with the high precision calibration samples and built-in software calibration procedures. Easy automatic tuning of the NMR frequency, pulse-durations, TX power and RX gain is included into the software package. 

Resonance Systems Ltd. has granted Process NMR Associates the rights to promote, market, and sell it’s NMR products and custom NMR hardware in the Americas, and Worldwide. The basic product of the company is a portable NMR-analyzer called Spin Track that can be used for many different low and high resolution NMR applications.

Spin Track meets the requirements of many relaxation and diffusion based NMR analyses:

Food industry (Solid Fat Content Analysis, Dairy Products, Oil and Moisture in Chocolate, Powdered Milk, Cheese and other food products; Oil and Moisture in seeds, Emulsion Characteristics)
Lipid Analysis – Fatty Acid Distribution
Cellulose and paper manufacturing (Moisture/Crystallinity Analysis, investigations of ageing effects)
Oil industry (rock cores analysis, oil-water, oil-water-gas, viscosity, physical property correlation, )
Polymer and rubber industry (Curing degree and elasticity analysis, polymer ageing, glass transition, amorphous/crystalline content)
Chemical industry (Density, Melting Points, Copolymer Ratios, Compatibility, Cure, Cross Linking, H or F content,
Medicine (NMR Surface Analysis of Patients, Plasma Analysis)
Environmental (Water Pollution, Forest Degradation, Soils, Fertilizers)
Fibers – Moisture and Finish Content
Pharmaceuticals (Tablet Analysis, Coatings/Components/Moisture, Hydrogen/Fluorine/Sodium Content)
Relaxation, Diffusion, Particle Size, Pore Size Distribution

Utilization of mobile NMR measurement equipment from Process NMR Associates provides the following advantages:

Reduction of expenses associated with meeting quality requirements of products
Simplicity of use in routine production measurements and in advanced laboratories for complicated analysis
Mobility of the hardware and low cost for the overall device
Non-invasive measurements of any sample
Hardware solutions for non-standard NMR applications
Permanent technical support and comprehensive scientific consulting
Fair price and absolute ease of operation!

Portable Low-Resolution NMR Analyzer

Analyzer is designed to perform:

All standard NMR applications
Development of new NMR-based techniques
Teaching quantum physics, NMR, analytical chemistry in Universities and Colleges

NMR analyzer Spin Track comprises functional parts (probes, preamplifier and duplexer, TX Power Amplifier, Sequence Generator and PC Interface, Data Acquisition System, NMR Transceiver) which can be purchased separately and used for the specific needs of an advanced customer (see example of connection assembly). Depending on the required magnet system the Spin Track can be used as NMR relaxometer or high resolution NMR spectrometer.

Basic characteristics of Spin Track analyzer:

Frequency range of the NMR spectrometer module: 5..60 MHz
Ringing time for 10 mm NMR probe is 8 ms
Probe tube diameter: up to 35 mm
Changeable preamplifiers and 50 Ohm matched duplexers with self bandwidth of 5 MHz
Customer-defined set of sensors (5, 10 and 30mm test-tube magnet systems, NMR surface sensors)
Adjustable TX output power up to 400 Watts
Adjustable RX channel gain up to 107
RX Sensitivity better than 1 mV (conditions: signal to noise ratio 3)
Adjustable digital filter bandwidth from 100 Hz up to 1 MHz
Pulse sequence length up to 64K events with resolution 100 ns
Quadrature 64Kx10-bit data acquisition system
Complete control of functions via personal computer – USB 2.0 Connectivity
Fast sensors replacement
Compatible with all Microsoft® Windows® operating systems

Software

The product software, Relax, is a powerful tool containing many standard NMR relaxation routines and applications, and can also be used to create new pulse-sequences, pulsed field gradients, gains and attenuations, post-processing methodolgies of considerable complexity. The built-in script language is based on a widespread Pascal syntax and is enriched with commands for fitting, Fourier and Laplace transforms, Low-pass filtering, etc. The script supports dialogue windows, static messages, user-defined diagrams, data manipulation procedures. Relax also allows direct processing of data obtained when utilizing Spin Track as a high-resolution NMR spectrometer.

Stationary Low-Resolution TD-NMR Analyzer

Analyzer is designed to perform:

Standard routine NMR applications
Development of new NMR-based techniques
Teaching quantum physics, NMR, and analytical chemistry in Universities and Colleges

The Spin Track Stationary fulfills all requirements to conduct NMR measurements like portable version of NMR analyzer.
In addition it is supplied with the possibility for increased probe volume to facilitate excellent statistical averaging of experimental results or to accomodate large samples.

Basic characteristics of Stationary Spin Track Analyzer:

Frequency range of the NMR spectrometer module: 5..60 MHz
Ringing time for 10 mm NMR probe is 8 ms
Probe tube diameter: up to 35 mm
Changeable preamplifiers and 50 Ohm matched duplexers with self bandwidth of 5 MHz
Customer-defined set of sensors (5, 10 and 30mm test-tube magnet systems, NMR surface sensors)
Adjustable TX output power up to 400 Watts
Adjustable RX channel gain up to 107
RX Sensitivity better than 1 mV (conditions: signal to noise ratio 3)
Adjustable digital filter bandwidth from 100 Hz up to 1 MHz
Pulse sequence length up to 64K events with resolution 100 ns
Quadrature 64Kx10-bit data acquisition system
Complete control of functions via personal computer – USB 2.0 Connectivity
Fast sensors replacement
Compatible with all Microsoft® Windows® operating systems
Relax Software

Educational Low-Resolution TD-NMR Spectrometer
Analyzer is designed to demonstrate NMR spin dynamics as well as provide a basic platform for undergraduate level chemistry and physics labs.
Standard routine NMR applications (FID, Spin Echo, CPMG, Carr-Purcell, T1-Determination (90-90 or inversion recovery))
Development of new NMR-based techniques – software allows development of pulse sequences by students without risk of instrument damage.
Teaching quantum physics, NMR, and analytical chemistry in Universities and Colleges

Basic characteristics of Stationary Spin Track Analyzer:
Frequency range of the NMR spectrometer module: 10..20 MHz
NMR Probe tube diameter: 5 mm
10-20 MHz Magnets, Surface NMR Sensors
Changeable preamplifiers and 50 Ohm matched duplexers with self bandwidth of 5 MHz
Adjustable TX output power up to 100 Watts
Adjustable RX channel gain up to 107
RX Sensitivity better than 1 mV (conditions: signal to noise ratio 3)
Adjustable digital filter bandwidth from 100 Hz up to 1 MHz
Pulse sequence length up to 64K events with resolution 100 ns
Quadrature 64Kx10-bit data acquisition system
Complete control of functions via personal computer – USB 2.0 Connectivity
Compatible with all Microsoft® Windows® operating systems
Relax Software

Custom NMR Components
For NMR engineers and advanced specialists Process NMR Associates offers accessories to upgrade, modernize, or build new NMR related devices (see connection example). All modules can be purchased separately and modules can be developed with unique characteristics to fulfill special requirements of the customer.

Surface NMR Sensors         NMR Sequence Generator

Data Acquisition Unit           Wide-Band NMR Transceiver

NMR Power Amplifier           NMR Pre-Amplifiers and Duplexers

For more information and pricing please contact John Edwards

Back to Process NMR Associates Home Page

The public forum site of the department of the interior related to the environmental impact statement is found at the following location. The site contains excellent overviews of the tar sands and oil shales found in Wyoming-Colorado-Utah. Excellent Oil Shale site from the DOE with strategic significance reports and government policy statements.

An interesting news article from Bruker world – “Bruker BioSciences Corporation Announces Agreement to Acquire Bruker Optics Inc. for $135 Million in Cash and Stock” dated April 17, 2006. Fascinating…. of particular interest from the process analytical and molecular spectroscopy side was Bruker Optics VP Dan Klevisha’s comment – ” For Bruker Optics, becoming part of a larger and public company will also allow us to explore complementary acquisitions.”

The Materials Research Society announces a call for papers for it’s Symposium (MM) on Magentic Resonance in Material Science to be held at the Fall Meeting in Boston on November 27 – December 1, 2006. Abstracts are due by June 20th.

There are a number of alternatives to buying new systems from Bruker-Varian-JEOL. A number of third party suppliers are present in the market selling and supporting refurbished used NMR systems. These companies can install and warranty the systems as well as maintain the cryogens for you if you wish. The companies that specialize in supercon NMR systems are Triangle Analytical, RS2D, NMR Associates, and MR Resources. A great place for used probes and repair is J S Research. Consoles can be obtained from Tecmag and from Anasazi (Anasazi also provides refurbished 60 and 90 MHz electro/permanent magnet systems). Spincore provides NMR spectrometer components for those who want to build their own instruments. Magritek, Minispec, Oxford Instruments, Resonance Systems, Progression, PCT, all sell TD-NMR instruments.

Process NMR Associates can guide you through this maze of choices.

Stan Sykora continues to expand his excellent NMR blog with two new articles on NMR signal reproducibility. His articles cover how field noise effects the repeatability of NMR signals such as FIDs and spectra and Hahn echoes and CPMG trains. In our experience of online NMR we have worked extensively on this topic with respect to the repeatability of the processed NMR spectrum and it’s effect on the repeatability/reproducibility of the chemometric predictions employed for process control. As Stan notes, if people have done a lot of work in this area it is certainly not being reported … mea culpa.

The Food and Agricultural Policy Research Institute has published it’s annual U.S and World Agricultural Outlook for 2006.

The University of Colorado Health Science Center installed a pumped 900 MHz system in 2005. They have an awesome video of a deliberate quench of the magnet as part of the ramping protocol. Here is the link to the video and here is a link to the NIH funded facility.

Edward Vawter of QD Information Services has made available two useful excel spreadsheets containing the 1H chemical shifts and 13C chemical shifts of most common deuterated NMR solvents. He also has a few other useful articles available from his download page.

Dylan Stiles at Stanford has an often hilarious blog category dedicated to the NMR aspects of his natural product synthesis projects. He gets a lot of commentary which is great as I think he has the only NMR blog that anyone cares to read. His blog is at http://blog.tenderbutton.com/?cat=9.

Phillip Grandinetti of Ohio State University (Research Group Site) offers an NMR post processing program for mac users called RMN at his website. He has an alpha version that runs under OS X and he is looking for alpha-testers to kick the tires. A more mature version is available that runs under Mac Classic OS.

 Mestrec laboratories also offer a cheap (50/100 Euro) software package that is available at iNMR.

The AMMRL (Association of Managers in Magnetic Resonance Laboratories) held an annual meeting at which a number of presentations were given that give an idea of the economics and issues that arise for University NMR Facility Managers and Administrators, the links are below:
Charlie Fry—Introduction
Ken Visscher—Open-Access Laboratories in Industry    
Nick Burlinson—Design and Installation of a Departmental NMR Facility
Eugene DeRose—Problems and Protections for Pumped Magnets   
Josh Kurutz—A Survey of Business Models for Academic Facilities  
David Vander Velde—Cryoprobes and Money (a.k.a. Losing Money) 
Klaas Hallenga—Practical Tips and Tricks with Cryogenic Probes

The AMMRL has a website with some basic information at http://chemnmr.colorado.edu/ammrl/ and has an invaluable archive of “user group” e-mails that discuss all aspects of running and maintaining an NMR facility (Email – Archives 1993-Present). If you have a question about instrument problems, instrument and cryogen maintenance, user training, user competency, safety issues, etc …. chances are the answers are already included in this database. The database can also be searched by key word to arrive at “on-topic” material.