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Summary
Contact:
John
Edwards
(203) 744-5905
| |
This page contains the
entire content of the PNA Blog Site
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.
Digital Spectrometers based on field
programmable gate arrays will soon change the face of NMR spectroscopy as a
routine use analytical instrument. Stan Sykora in his excellent blog (http://www.ebyte.it/stan/blog07.html#07jun14)
describes how the transition of NMR spectrometers to digital electronics has
drastically reduced the footprint and price of NMR spectrometers and
increased the potential complexity of the RF synthesis as well as the NMR
post processing on the same chip. In fact single chips can hold multiple
spectrometers enabling the building of single spectrometers that can perform
experiments on multiple magnet systems.
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.
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
“reaction” to the typical “supercon” NMR lab. We are introducing a
continuous flow NMR system that can be on the benchtop. The system uses a
high resolution 60 MHz 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.
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.
Simple Reaction Chemistry
Presented here are several simple reactions
monitored by 60 MHz process NMR performed in a 5 mm NMR tube.
Reaction #1: Acetic Anhydride in Water –
Reacts to form Acetic Acid
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
Second Reaction was Performed with a
vigorous shake of the NMR tube before observation.
For More Information Contact John Edwards
These are non-spinning spectra obtained on a
Qualion process NMR spectrometer operating at 58 MHz. The spec on water at
this shim level is 1.5/5/20 Hz at 50%/10%/0.5% peak height. The first
spectrum is of 91% isopropyl alcohol in water – store bought pharmacy
product. The second spectrum shows the comparison of a 300 MHz 1H NMR
spectrum of Advil compared to a non-spinning 58 MHz spectrum.
Presented at Marist College, Poughkeepsie
September 23, 2009
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.
Bio:
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.
Topnir Systems is proud to announce the signature in
October 2009 of a Partnership Agreement with Process NMR Associates, LLC.
This partnership enables Process NMR to utilize our field
proven software in complementary fields NMR and MIR combining forces to
deliver total solutions with increased added value to customers.
Topnir Systems is a French company leader in the field of
online Near InfraRed (NIR) analyzers. Topnir enables measuring and
monitoring multiple hydrocarbon streams in less than one minute using a
single online system. The company has a long history in the refining and
petrochemicals business, being the first world wide to implement an online
application designed to measure and control octane number for gasoline
production, first NIR on-line application worldwide on Ethylene Plant
Naphtha feed (1986), Gasoline (1989) and Crude (1991). The business started
in the late 80s within BP Oil, with applications development around gasoline
and diesel blending, as well as FCC, CDU, Reformer and Ethylene plant feed
andproducts characterization. Major oil companies such as Shell, BP, Repsol,
Aramco… have adopted Topnir solutions.
Topnir has recently expanded its activities to provide
platform independent software for NIR systems already installed in the
field. Topnirs modeling technology offers a full set of properties from a
single model which offers the advantage of a robust, reliable system
requiring very light maintenance. In addition Topnir is field proven to have
ASTM and better results.
Process NMR Associates, LLC is an American company and
leader in the field of online Nuclear Magnetic Resonance (NMR) process
applications. The company also has a long history in the refining and
petrochemicals business, being the first world wide to implement online NMR
applications for gasoline and diesel blending, FCC, CDU, Reformer and
Ethylene plant feed and products characterization.
Topnir Systems SAS
425, rue RenéDescartes
Espace Descartes, Bat C
Parc de la Duranne
13857 Aix-en-Provence, France
Tel +3350 73 47 / Fax+3350 73 50
Web: www.topnir..com
USA Contact: Julie Williams
Tel: +1-508-736-2696
Process NMR Associates, LLC
87A Sand Pit Road
Danbury, Connecticut 06810 USA
Tel +203-744-5905
Fax +203-743-9297
Web: www.process-nmr.com
Contact: Dr. Paul Giammatteo
Paul Giammatteo recently presented two papers at the Gulf
Coast conference that was held in Galveston, Texas on January 20-21.
His first paper was entitled “Counting Carbons for
Tighter Control: Combining GC and NMR to Improve Distillate Manufacturing”
and centers on the topics of Simulated distillation correlated to 1H NMR.
The second paper was entitled “Analytical Data For
Engineering Support: Improving the Lab/Process Interface”. This paper
details the development of a series of heavy petroleum applications on a
Smiths Detection FTIR-ATR spectrometer.
PDFs of the presentations can be obtained from the
following links: 1) NMR
Talk 2) FTIR-ATR
Talk
Alginate is a linear polysaccharide composed of mannuronate (M) and a-L-guluronate
(G). The polysaccharide is characterized by the relative ratio of M/G,
G-Content, and average length of blocks of G in the polymer. M and G are:
ASTM F2259 recounts the standard sample preparation and 1H NMR analysis
that allows the following parameters to be calculated:
The 1H Spectra obtained on a typical alginate sample are show below:
Finally the peaks representing the individual M and G components and
sequences are deconvoluted from the spectrum.
The intensities obtained from the deconvolution are input into the excel
spreadsheet shown above and the various ratios, M and G content and a series
of diads and triads are calculated along with some G block lkength
information. It is the block length information that often reveals telling
differences between samples.
Process NMR Associates performs this analysis at a cost of $225 per
sample. The samples, however, must be prepared by the customer using the
methodologt set forth in the test method.
Over the past few years balsamic vinegars have been the
subject of a number or NMR studies to determine authenticity, degree of
aduleration, and age. 1H NMR has been used to quantify the relative
concentrations of a series of organic components (ethanol, fructose,
glucose, acetic acid, succinic acid, lactic acid, butandiol, etc (ref 1).
13C NMR has been used to determine the aunthenticity and degree of
adulteration (ref 2) as well as the length of the ageing process that a
given sample has undergone. Also the formation of glucose and fructose
acetates during maturation and ageing has been studied by 1H and 13C NMR.
Refs.
1) Caligiani et al., Anal. Chim. Acta, 585 (2007) 110-119
2) Consonni et al., Talanta, 75 (2008) 765-769
3) Consonni et al., Anal. Chim. Acta, 611 (2008) 31-40
4) Consonni and Caligiani, Talanta, 73 (2007) 332-339
5) Cirlini et al, Food Chemistry, 112 (2009) 51-56
The concentration and distribution of the organic
components has been found to correlate well with ageing process analysis,
identification of adulteration, and determination of authenticity of
traditional balsamic vinegars and balsamic vinegars of Modena.
Below are a series of spectra showing what can chemistry can be quantified
in the balsamic vinegars as well as a few comparative spectra of apple cider
vinegar and malt vinegar.
For comparison with the home made ciders analyzed in the previous posting
I am including the NMR of analysis of a commercial pear cider. The previous
ciders were very dry while the pear cider was decidedly sweet. The
carbohydrate content is a notable difference. The 1H spectrum is shown with
chemical components identified.
October
31, 2008
There
have been quite a lot of NMR studies centered around apple cider
(non-alcoholic) and apple cider vinegar. However a search of the literature
turns up no reference for NMR analysis of hard apple cider. This effort was
undertaken to analyse the alcohol content of the ciders and to determine the
malic and acetic acid content. Ciders were produced by Dr Tim McMahon of
Orange Community College, NY….for his own consumption.
Below
are the NMR spectra obtained by regular 1H acquisition and with BINOM
solvent suppression.
Data
was obtained on our Varian 300 MHz spectrometer. Samples were prepared by
degassing followed by addition of 1 drop of D2O as lock solvent.
Process NMR Associates, LLC (Danbury CT) and Active Spectrum, Inc (San
Carlos CA) are collaborating in the application of micro-ESR technology to
petroleum applications. The initial work has focussed on crude oils but will
soon be expanded to residues and cracker feedstocks.
Five samples of crude oil were tested by Micro-ESR spectrometry. The
samples were:
1. Vasconia, Magdalena Basin, Columbia (V=39 ppm)
2. Merey, Eastern Venezuela Basin, Venezuela (V=303 ppm)
3. Oriente, Oriente Basin, Ecuador (V=65 ppm)
4. Qua Iboe, Agbada Formation, Niger Delta (V=2 ppm)
5. Basrah Light, Zubair Zone, Iraq (V=29 ppm)
The following spectra were observed:
Figure 1: Micro-ESR Spectra of Crude Oil
The central peak is a combination of a persistent carbon-centered organic
radical (g = 2.003) found in asphaltenes, and a vanadyl (VO2+) peak. The
additional smaller peaks are associated with vanadyl only.
For producers, the technique could be used to rapidly measure asphaltene
concentration on-line. The spin density of the organic radical is a function
of the maturity of the oil and will of course vary between deposits.
Notwithstanding, rapid electronic measurement of asphaltenes remains a topic
of great interest. Similar techniques have also been used to assess the
quality of coals. For refiners, vanadium is a contaminant that poisons the
refinery catalyst. ESR has been used by refiners since 1962 to rapidly
measure vanadium content in crude oil feedstocks both on-line and in
laboratories. Active Spectrum Inc.’s Micro-ESR is shown below. It is
2.25″ in diameter by 2.5″ high. Power input is 12-30VDC, and the
data interface is USB. The device is available as either an on-line sensor
or as a benchtop unit.
Figure 2: Micro-ESR Sensor
Figure 3: Higher Homogeneity Spectrum of Merey Crude
Micro-ESR is complimentary to NMR in that it observes paramagnetic metals
and organic radicals which are unobservable by NMR. The stable free radical
signal is indicative and quantitative to the amount of asphaltenes in the
crude oil sample and vanadium metal content is an important processing
parameter for cracking processes as it is active in the passivation of
catalysts. NMR on the other hand observed the detailed hydrocarbon chemistry
of the sample and yields chemico-physical parameters such as aromaticity,
paraffinicity, naphthenicity, distillation, density, PAH distribution. In
combination these two technologies yield a detailed picture of the petroleum
materials before and during the refining process.
Samples provided by John Edwards of Process NMR Associates, LLC. Micro-ESR
analysis provided by James White of Active Spectrum, Inc,
Active Spectrum, Inc. 110 Glenn
Way #15, San Carlos, CA 94070 650-610-0720 | 626-628-1970 f | activespectrum.com
Process NMR Associates, LLC. 87A
Sand Pit Rd, Danbury, CT 06810 203-744-5905 | 203-743-9297 f | process-nmr.com
PDF
Version of Application Note
For more information contact John
Edwards (203) 744-5905
Current Technique for Feedstream Analysis:
Analysis Performed – Refractive Index, Distillation, Specific Gravity
Calculation Obtained – Watson K-Factor
Outcome: aromatic carbon number, aromatic hydrogen number, total hydrogen
content
Proposition: Detailed hydrocarbon analysis for kinetic model development.
Our experience is that an improved and useful analysis can be obtained
from NMR
analysis. There are several ways to approach the NMR analysis and the
chemometric approach to correlating NMR data to physico-chemical parameters
of
use to process control.
RCC Feedstream Analysis by 1H and 13C NMR: Multivariate Prediction of
Chemical and Physical Properties
Presented at the 236th ACS National Meeting, Philadelphia PA, August
17-21, 2008
John C. Edwards Ph.D.
Process NMR Associates LLC
87A Sand Pit Rd, Danbury, CT 06810
Jincheol Kim,
SK Energy Co., Ltd, SK Energy Technology Center,
140-1, Wonchon-dong, Yuseong-gu, Daejeon 305-712, Korea
Summary of Slides
1) 60 MHz process NMR data available from online NMR unit.
2) 300 MHz 1H NMR data available from standard NMR experiments on
laboratory NMR system at Process NMR Associates
3) Expansions of 1H NMR data on RCC Feeds
4) Calculated 1H NMR Parameters Represented as an alternative
“spectrum” for use in chemometric modeling and linear regression.
5) 13C NMR Data obtained on RCC Feeds
6) Expansions of 13C NMR Data
7) 13C NMR and Average Molecule Parameters Calculated from 13C Spectrum
Calculated 13C NMR Parameters Represented as an alternative “spectrum”
for use in chemometric modeling and linear regression.
9) Correlations of Spectra and Calculated Parameters to Physico-Chemical
properties of RCC Feeds
10) Correlation of Spectra and Calculated Parameters to Density
11) Variable Selection for Linear Correlation of Calculated NMR
Parameters to Physico-Chemical Properties of RCC Feeds.
12) Correlation of Calculated 13C NMR Parameters (C-Type and Average
Molecule) with both high resolution 1H and 13C NMR spectra. Models created
can be utilized by personnel with no NMR experience to calculate NMR
parameters directly from the spectrum without any prior knowledge of
integrations or calculations to be performed.
Summary
Chemical and Physical Properties of RCC Feedstreams can be determined
by 1H NMR (at 60 and 300 MHz) and by 13C NMR
H-Type and C-Type Parameters do not provide as good a correlation as is
observed
by full spectrum regression. This is due to loss of resolved chemical shift
information
when the spectrum is reduced to larger integral areas.
1H NMR can be combined with PLS regression modeling to provide detailed
carbon
type analysis for RCC Feeds
Regression analysis of 13C NMR data can be utilized to fully automate the
prediction
of 13C NMR type analysis : reducing the necessity for considerable knowledge
and
analysis time on the part of the analyst.
For further Detail Contact John
Edwards
Diesel Production Control - Combination
of NMR and Simulated Distillation to Yield On-Line Carbon Number Distributions
Process NMR Associates has developed a
database of Simulated Distillation database on a large number of diesel fuels on
our Shimadzu 2010-GC with SimDis Software. The analysis is being used to develop
distillation prediction models for the process NMR systems as well as explore
new avenues of control information that can be derived by combining carbon
number distributions obtained from the GC data with the predictive capabilities
of online NMR.
For a PDF version of this application
article download this: Combination
of NMR and Simulated Distillation for Diesel Production Control
Simulated distillation allows carbon
number distributions to be calculated and in combination with chemistry observed
in the NMR analysis the effect of aromatics and olefins on the paraffin
distributios can be estimated. Online NMR predictions can be established that
yield real-time carbon number distributions for production control and sulfur
species monitoring.
Contact: Paul Giammatteo at paul@process-nmr.com
or +1 (203) 744-5905
Extensive
NMR Diesel Database Enhances NMR Model Performance for Unit Control and
Product Manufacturing
An extensive database (10
years) of diesel samples incorporating all refining processes
(distillation through product blending) enables development of robust,
wide ranging property predictions independent of crude sources and
refinery processing. Consistent attention to data integrity enables
expanding model ranges well beyond any typical single unit or process
operation. The following slides elucidate the consistency in spectra
whether obtained 10 years ago or last week, from within a refinery or on a
laboratory spectrometer.
For a PDF version of this
application article download this: NMR
for Diesel Production Control
If you are interested in discussing the
applicability of NMR to diesel production control do not hesitate to
contact us at (203) 744-5905 or at paul@process-nmr.com.
September
15, 2008
Here
is an example of a 1H NMR analysis of a 2007 Red Wine submitted for chemical
analysis by John W.
If
you are interested in wine analysis please contact us.
Over
the past 20 years we have obtained the solid-state NMR analysis of pretty
much every carbonaceous material that exists - including coal/oil shales/bitumen,
polymers/catalysts/fibers, cellulose/polysaccharides/foodstuffs/gels,
deposits/dried sewage/meteorites/soils/clays, etc. With the increased
attention to coal liquifaction and gasification technologies we have
developed an interest in creating an NMR database for coals. Coals were
obtained from the Penn
State Coal Sample Bank at
a very reasonable cost. We have performed CP-MAS, DD-MAS, Variable Contact
Time, and T1 inversion recovery experiments on all the samples. We are
currently developing regression relationships between the NMR data and the
physical and chemical testing data that is provided with the samples. At
some point we will write this up as a journal article. Here are some
snippets of data from the coal analysis along with a few results obtained on
the menagerie of samples we look at on any given day including some oil
shales, engine deposits, refinery coke, asphaltenes, and pipe tobacco.
Please
inquire if you are interested in the details of the above analyses.
September
13, 2008
Process
NMR Associates and Spin Resonance Ltd have recently completed the
construction a small 60 MHz (1.4T) 5mm TD-NMR system that can be utilized to
study T1 and T2 characteristics of novel contrast agents at typical MRI
frequencies. Here are a few pictures of the magnet. It is based on N42
neodymium-iron discs (120mm diameter x 30 mm deep).
February
28, 2008
NMR
Process Systems – Integrated Solution
Application
for Crude Unit and Downstream Processes:
Spectro-Molecular Control for Enhanced Diesel Recovery
NMR
Process Systems’ (NPS) on-line NMR based analytical and process control
strategy for enhanced diesel recovery at the crude distillation unit
maximizes clean diesel recovery by enabling closer cut point control in the
mid-section of the CDU.
Clean
Fuels regulations in both the European and American markets have had a
substantial impact on a refiner’s ability to maximize product draws at the
refinery front end. Extremely low sulfur requirements for gasoline and
diesel have resulted in refiners now being more constrained at the
hydrotreaters. Lack of reliable, focused, measurement and control of
critical CDU product draws has forced many refiners to significantly
undercut these draws in order to ensure minimum error in the final product
blends, especially with respect to total sulfur. Depending on a refinery’s
crude supply and CDU capacity, a conservative estimate of 300-500+ barrels
per day of loss diesel production is typical. With an average of $25-$35 per
barrel margin loss, the economic impact of these Clean Fuels Regulations are
substantial.
Integrating
proven NMR technology with a focused measurement and control strategy
enables crude unit operations to cut “chemically” closer to the
hydrotreater constraint limit. The strength of NMR is that it quantitatively
and accurately “observes” the chemistry of each refinery stream and
readily relates that chemistry to chemically dependent parameters such as
distillation, cetane, freeze points, etc. The NPS strategy is to cut and
control CDU diesel production as closely to the dibenzothiophene
distillation limit as possible. Figure 1 illustrates this strategy in terms
of both current and proposed NMR based measurements.
Figure
1: Overall NMR measurement and control outline highlighting
measurement/control strategies.
Let
NMR Process Systems deliver “Spectro-Molecular” Control to your refinery
so that you can achieve real economic and production benefits.
January
28, 2008
Just
came across an old presentation on gasoline analysis by NMR and chemometrics
with direct comparisons to Mid-IR and NIR. Presented at the Experimental NMR
Conference in March 1996….PDF (3
MB)
Conjugated
diolefins are responsible for fouling of many processes in a refinery. COSY
NMR analysis can determine the concentration of these species in many
processed petroleum product streams….see
PNA webs site.
October
29, 2007
Title:
Process Analytical Technology (PAT) Manager
Description:
Implement Process Analytical Technology (PAT)
throughout all the Global Quality Sites to identification of incoming
materials and monitor manufacturing processes.
Work directly with the sites and Schering Plough Research Institute to help
support / initiate the development, validation, and deployment of PAT at the
sites.
Review, evaluate, implement, and manage PAT activities.
Provide guidance / technical help to the sites to conduct evaluation and
purchase commercial PAT related analytical equipment (e.g. NIR / FT-NIR,
Raman / FT-Raman, IR / FT - IR etc.).
Maintain analytical instruments in the lab to comply with cGMP standards and
requirements.
Train and mentor laboratory staff on PAT to generate analytical data for
routine experiments.
Generate network and infrastructures with various sites of the corporation.
Take full ownership / responsibility and provide effective, meaningful,
result driven and pro-active leadership on all PAT projects.
Responsible to transfer knowledge / technology of PAT related projects and
activities to sites. Job is located in New Jersey.
Respectfully, Vincent
L. Graziano
Recruiting Manager
/ Global Staffing
Schering-Plough
Corporation
556 Morris Avenue,
S1-1
Summit, N.J. 07901
Ph: 908-473-2745
Fx: 908-473-2793
Ph: 908-298-5232
(Kenilworth)
Careers: Employment
Opportunities
email: vincent.graziano@spcorp.com
Press
Release -
NMR Process Systems - Swagelok
Technology Conference, Teaneck NJ - October
23, 2007
NMR
Process Systems, LLC Announces : NPS-IS© - NPS
– Integrated Solutions
NMR
Process Systems (NPS) announces a new era in advanced analyzer and process
control solutions for on-line and at-line process applications. NPS’s
Integrated Solutions (NPS-IS©) approach is designed to take
advanced on-line analysis to the next level in delivering real engineering
and economic benefit to the user.
NPS-IS©:
the first and original source for any and all on-line NMR applications
regardless of NMR vendor.
NPS-IS©:
the first to offer integrated advanced analytical solutions using multiple
technologies “in one box”.
NPS-IS©:
the first to offer a fully integrated Swagelok sampling solution for
improved sample switching and reliable measurement.
Too
many spectroscopic based on-line analyzer projects (FTIR, NIR, NMR) have
failed to meet expectations and/or objectives due to:
· Overselling
the measurement
· Underestimating
the sampling requirements
· Trying
to replace all traditional analyzers with one technique.
NMR
Process Systems is positioned to deliver the real benefits of advanced
analytical systems in petroleum, petrochemical, chemical, food and beverage
and pharmaceutical applications. Moving beyond the traditional
replacement analyzer philosophy, “NPS-IS©” integrating
analyzers and advanced controls to deliver real process improvement and
economic benefit. Such integration leverages the strength of any individual
spectroscopy, shortens per stream analysis time, and builds in internal
cross-checking to ensure accuracy.
For
more information contact Paul
Giammatteo Principal,
NMR Process Systems
87A
Sand Pit Rd, Danbury, CT 06810 U.S.A. Tel: (203) 744-5905
Press
Release -
NMR Process Systems - Gulf
Coast Conference, Galveston Island, Texas - October
17, 2007
NMR
Process Systems, LLC and Smith’s Detection Launch RefinIRTM -
The New Refinery Products Analyzer
In
a joint development effort NMR Process Systems and Smith’s Detection have
developed a range of petroleum analyzer products based on a mid-infrared
spectrometer which utilizes an attenuated total reflection (ATR) sample
interface. The ATR allows wipe and swipe sample introduction that is ideal
for heavy petroleum analysis. Chemometric approaches to chemical and
physical property prediction have been developed as well as analysis by
spectral database matching. The FTIR-ATR spectrometer is called the RefinIR
which can be utilized in the laboratory for rountine, multi-parameter
prediction of petroleum product properties or to aid in process
troubleshooting on unusual samples or solid foulants.
For
more information contact Paul
Giammatteo Principal,
NMR Process Systems
87A
Sand Pit Rd, Danbury, CT 06810 U.S.A. Tel: (203) 744-5905
In
a joint development effort Process NMR Associates and Resonance Systems Ltd
have developed a replacement NMR spectrometer for the Oxford QP-20 TD-NMR
analyzer. In many cases the excellent magnet and probe of the QP-20 continue
to work effectively long after the NMR spectrometer has died. The Spin
Track-20 spectrometer enables the user to completely replace the QP-20 NMR
system while retaining the use of the original magnet and probe
configuration. The product represents state-of-the-art digital NMR
technology allowing newly developed TD-NMR methodologies to be applied to
complex systems with all the advantages of a windows computer system
(replacing the paper cartridge of the original system). Customers who have
malfunctioning QP-20 NMR systems can obtain a modern digital NMR system
within 8 weeks of order and for less than $16,000. The modular design of the
Spin Track TD-NMR systems allows our engineers to develop replacement
systems for all benchtop NMR systems such as those marketed by Oxford
Instruments, Bruker Minispec, and Resonance Systems. Contact us if you have
a non-functioning system that might be a candidate for the Spin Track
upgrade.
For
more information contact John
Edwards Principal,
Process NMR Associates - Spin Track Division
87A Sand Pit Rd, Danbury, CT 06810 U.S.A. Tel: (203) 744-5905
October 5, 2007
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 21st 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.
June 12, 2007
NMR
analysis of Jasmine Absolute.
For
more information on NMR of Essential
Oils visit the PNA website.
May 15, 2007
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
May 14, 2007
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.
May 10, 2007
I am posting this on behalf of Damien
Jeannerat.
PhD
Position Available Starting in September
2007
April 16, 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.
April 15, 2007
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
April
14, 2007
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
April
13, 2007
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
|
Solids
13C CPMAS
|
Normalized
to Reg 3
|
|
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
March
30, 2007
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”
March
25, 2007
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
March
24, 2007
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).
February
7, 2007
Press
Release
- NMR Process Systems - Danbury
CT -
February 14, 2007
Dr
Edwards of Process NMR Associates has
been asked to organize a session on
Process NMR Technology at the Eastern
Analytical Conference to be held at
the Garden State Exhibit Center,
November 12-15, 2007. Below is a copy
of the Call for Papers sent out on
February 14, 2007.
Hello
to all,
I
have been asked by Cecil Dybowski to
chair a session on Process NMR
Technology at the 2007 Eastern
Analytical Symposium to be held
November 12-15 at the New Jersey
Garden State Exhibit Center in
Somerset New Jersey. At this point I
am putting out some feelers to gauge
the level of interest that is out
there amongst NMR practitioners in
this field. I would like the session(s)
to encompass both high resolution and
time-domain applications of NMR in
process control applications and
at-line in manufacturing facilities in
all industry sectors. The work can be
actual on-line examples or laboratory
based analysis being used to justify
or prove applications before they are
spun out to the plant. Developments in
hardware, software and chemometrics
would also be of general interest and
to this end hardware talks on magnet
and NMR-sensor development and their
potential application would be
encouraged. Fully automated NMR
analysis in the laboratory that simply
requires a technician to load the
samples would also be considered as a
valid topic.
The
abstract deadline for EAS is April
15th. If you are interested in
presenting a paper I would appreciate
hearing from you by e-mail. Once I
know how much interest is out there I
will begin pulling the details
together and have the speakers submit
abstracts through the EAS website. For
your information the EAS is the
premier analytical meeting for the
U.S. East coast and it has a website
at http://www.eas.org.
Also, as an introduction to the
symposium itself, I am providing a
link to the program chairs letter - http://www.eas.org/symposium/symposium.html
The
distribution I have included in this
e-mail are of persons and
organizations that I know are working
in this field. If you have any
colleagues, customers, or
acquaintances who you feel could
provide a good presentation on their
research or applications please feel
free to forward this e-mail on to
them, or inform me of their e-mail
address and I will contact them.
I
look forward to hearing from you and
hope that you will join us in New
Jersey,
Best
Regards,
John
Contact
: John Edwards, (203) 744-5905
E-Mail: john@process-nmr.com
January
22, 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.
Abstract
The
Wonderful World of Non-Traditional NMR
Spectroscopy
Over
the past 60 years NMR has developed
into a premier spectroscopic tool in
the academic and industrial world.
Superconducting spectrometers with
fields ranging from 7 to 23 Tesla are
considered as typical NMR equipment
and NMR “cold probes”, operating
at near liquid Helium temperatures,
are now hot items to improve
sensitivity and throughput. NMR
technology has also found other
application areas to exploit and these
areas are a far cry from a laboratory
environment. Permanent magnet based
NMR systems are currently used to map
the underground hydrocarbon-water
makeup of oil drilling wells and to
control huge production units in
refineries and chemical plants based
on observed proton chemistry. Portable
NMR systems are taken into the field
for on the spot analysis of
agricultural products, antarctic ice,
elastomer performance, concrete and
wood moisture analysis. Single-sided
NMR probe/magnet sensors are being
used to study degradation of antique
books, frescoes, and paintings. The
non-traditional NMR technology and
applications will be described and the
economic benefits of the applications
will be discussed. The future of NMR
will include small, affordable,
automated systems that will make NMR a
much less exotic technique reserved
only for large budget industrial or
academic facilities.
Contact
: John Edwards, (203) 744-5905 E-Mail: john@process-nmr.com
January
19, 2007
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
December
28, 2006
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
December
6, 2006
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.”
September
28, 2006
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
Endorsed
by the Colorado Section – American
Chemical Society and the Rocky
Mountain Section – Society for
Applied Spectroscopy
Related
Links:
5th
Alpine Conference on Solid-State NMR
11th
Brazilian NMR User
Meeting / Workshop: NMR
in South America – May 7-11, Rio de
Janeiro State, Brazil
For
information please contact Sonia
Cabral de Menezes
45th
Annual Meeting of The NMR
Society of Japan Nov.
22-24, Kyoto, Japan
MRS
Symposium “Magnetic Resonance
in Material Science” Nov.
27 – Dec. 1, Boston, Massachusetts, USA
For
further NMR
meeting info visit http://www.process-nmr.com/meetings_and_events%202006.htm
September
27, 2006
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.
September
25, 2006
Yet
another masterpiece from tenderbutton
– NMR
of earwax.
September
19, 2006
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.
September
15, 2006
I
was at the SMASH
conference in Burlington Vermont
earlier this week and the presentation
of the week in my opinion was the
multi-sample MAS
probe poster by Nelson et al. This is
a probe based on a patent (6,937,020)
filed by Professor Eric Munson’s NMR
group at the University of Kansas, and
built by David Lewis of Revolution
NMR. The
concept involves stacking multiple MAS
rotor housings in the probe head and
then shuttling them into the central
sweet spot of the magnet for
acquisition via a pneumatic device
attached at the base of the probe. The
RF is switched between independent RF
inputs and each housing has an
independent tune/match capability. The
idea is to increase throughput by
allowing extra acquisitions to be
obtained on other samples during the
relaxation delays of the independent
experiments.An excellent video
demonstration is available on the webpage
dedicated to the probe, as well as
references to the patent
and the journal article covering the
development (“Multiple-sample probe
for solid-state NMR
studies of pharmaceuticals”, Solid
State Nuclear Magnetic Resonance 29
(2006), 204 – 213). Commercial
release is expected in 2007.
July
28, 2006
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.
July
21, 2006
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.
July
19, 2006
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
A new
joint venture between HTS-110
and US company Progression Inc will
provide customers with a unique high
temperature superconducting (HTS) magnet
capability.
1
May 2006
HTS-110
Limited, an affiliated company of
Industrial Research, focuses on HTS
solutions for medical, scientific,
energy, defence, transport and
industrial markets. Progression is a
world leader in the development and
implementation of process Nuclear
Magnetic Resonance (NMR) technologies,
Laser Induced Breakdown Spectroscopy (LIBS)
techniques, and Laser Induced
Fluorescence (LIF) analysers for the
mining, petrochemical, and
polymer/polyolefin industries.
The new
venture, Progression-HTS-110, will
provide customers with unique high
temperature superconducting (HTS) magnet
capability. The new series of analyser
will operate at 80MHz with the field
strength of 2 Tesla generated by a HTS
magnet.
Target
markets for the analyser will include
refining applications in the oil and gas
industry, educational research and
development, pharmaceutical and
biochemistry applications.
Chief
executive of Progression, Vaughn E.
Davis, says the company is looking
forward to working with HTS-110
Ltd and describes the deal as the
perfect complementary vehicle to extend
and build on the unique strengths of
Progression’s leading market position
in process NMR.
Chief
executive of HTS-110,
Dr Sohail Choudhry, says it is a
strategic move to partner with
Progression and extend HTS-110’s
leading-edge technology into new
markets.
“HTS
is an advanced and rapidly developing
new technology and we look forward to
using that as a key driver for expanding
the marketplace with Progression.
“Progression
is an innovative company and we share a
similar culture – that will work to
our advantage and allow us to benefit
from both our unique and complementary
skills.”
It is
anticipated the new company will be
headquartered in Houston, Texas, under
the leadership of Mr. Scott Simmons.
HTS-110
is a subsidiary company of Industrial
Research Ltd – it’s HTS
magnet technologies are described here.
July
17, 2006
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 .
July
13, 2006
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.
July
11, 2006
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.
July
3, 2006
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
June
19, 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
June
1, 2006
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.
May
31, 2006
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.
May
30, 2006
I guess you
learn something everyday… The
Harrison R. Cooper Systems Company
of Bountiful Utah has been marketing
low field Phosphorus-31
and Fluorine-19
NMR analyzers for a phospate
mineral benefication process and
for fluorine monitoring in mineral
slurries. It appears from the site
that only a few installations were made
and no indication of successful outcomes or
benefits are provided in the analyzer
and process descriptions. I can’t
decipher where the NMR
technology originated….perhaps Auburn?
May
26, 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.
May
22, 2006
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.
May
18th, 2006
Dr Joseph
Vaughn of Florida State University has
placed an autopsy of a Varian R2D2
7.05 Tesla NMR
magnet on the department website. The
innards of the magnet and probe are all
exposed in the gory photographs. Check it
out at the FSU
chemistry site : http://www.chem.fsu.edu/facilities/cutaway_nmr_magnet.asp
This is
one of the siblings of the magnets that we
operate in our labortory at Process
NMR Associates.
The site is only for those with a strong
stomach.
May
16th, 2006
This
conference (MRPM8)
will be held September 10-14 at the
University of Bologna, Italy. It is being
held a few days after the 6th Colloquium
on Mobile magnetic Resonance in Aachen
Germany, (September 6-8, CMMR6)
to facilitate the attendance of conferees
at both meetings.
May 3rd,
2006
Symbion
Systems Inc has developed a family of
software products that provide a common
interface for communicating with,
networking, and controlling many analytical
instruments, and sample systems, in a
laboratory or process analysis setting.
The software can control many individual
analyzers from different vendors, process
the data and visualize it, store the data
in SQL
databases, and perform complex chemometric
analysis by calling various
calibrations from many chemometric
software platforms. The predictions
obtained from process analytical
instrumentation can be plotted,
visualized, stored, and outputted under
many standard formats for integration with
process control and optimization software.
A version can be obtained that is GLP/GMP/21
CFR, Part 11
compliant. The software will provide an
excellent platform for development and
execution of analytical laboratory
methods, as well as process analytical
applications.
May 3rd,
2006
Bruce
Johnson of One
Moon Scientific (ex Merck) has
produced a series of software tools for
visualizing and analyzing spectroscopic
data with particular emphasis on NMR
data. His NMRViewJ
can process and visualize NMR
datasets in 1 or multiple dimensions and
has built in molecular visualization and
statistical data analysis tools. The
software is “free” but Bruce asks that
if you download and use it you should pay
a “support contract fee” in order to
support the ongoing development of the NMR
software products.
April
26th, 2006
The
International Society of Magnetic
Resonance announces the 16th Triennial Conference
to be held at Kenting, Taiwan, October
14-19, 2007. Organized by the Taiwan
Magnetic Resonance Society, Academia
Sinica, Taiwan – Website is found at http://www.ismar2007.sinica.edu.tw/
March
14th, 2006
Dow
Corning have published a small overview
paper on manufacturing processes and
development of silicones in pharmaceutical
formulations. The paper includes
characterization details by FT-IR and NMR.
March
14th, 2006
The 6th
Colloquium on Mobile Magnetic Resonance has
now posted an official website to cover the
meeting at http://www.cmmr.de/index.htm
March 13th,
2006
Hamden, Conn.
– Dr. Paul J. Giammatteo, co-founder of
Process NMR Associates,
will present “Pulse, Acquire, Control: Ten
Years of Online High-Resolution Nuclear
Magnetic Resonance (NMR) in Refining,
Petrochemical and Food Manufacturing” at 12
p.m. on Monday, March 27, in the Clarice L.
Buckman Theater at Quinnipiac University.
The free
lecture is open to the public and is part of
Sigma XI Special
Seminar Series.
From gasoline
manufacturing to butter production, more than
140 online NMRs have been placed in
manufacturing plants worldwide. Giammatteo
will discuss installation and utilization of
this technology, its application in the
petroleum and petrochemical industries and the
future in pharmaceuticals.
Giammatteo
co-founded Process NMR Associates,
based in Danbury, in 1997. He previously
worked for Texaco for 17 years. Giammatteo
received his doctorate in chemistry from
Wesleyan University and has published and
presented more than 30 papers.
For more
information, contact James Kirby, associate
professor of chemistry at Quinnipiac, at (203)
582-8275 or James.Kirby@quinnipiac.edu
March 10th,
2006
March 10th,
2006
A handy
calculator from BP allows you to calculate
your impact on global warming – Carbon
Calculator.
March 9th,
2006
Ultrafast 2D NMR
spectroscopy obtained in a single scan is
described by Lucio Frydman of the Weizman
Institutein his paper entitled “Single
Scan 2D NMR”
March 9th,
2006
Professor John
Lindon (Metabometrix Ltd) provides an Overview
of Metabonomics relating the role of high
field 1H NMR in
metabolite profiling in biofluids.
March 1st,
2006
A strange CPACT
NMR project development – DECRA
processing of FID data
- this involves quantitative analysis of FID
signals in order to avoid automated phasing
routines – in our process NMR
experience phasing is a critical issue in the
reproducibility of online NMR
data, however, it is not an unsurmountable
problem that leads to the development of new
processing techniques such as those described
here. Robust, repeatable phasing algorithms can
be developed and implemented.
March 1st,
2006
The
Oil Drum is a blog dealing with the
impending global problem of Peak
Oil Production also called “Hubbert’s
Peak” – or should we say Peak “Easy”
Oil Production.
Other sites that cover this topic are: Peak
Oil News, Peak
Energy, Past
Peak (A little bit anti-Bush), and Peak
Oil.Org.
Fossil fuel
developments in Oil Shale, Tar Sands, and Coal
Liquifaction will have to replace the “Easy
Oil”. At $70 per barrel these are all
plausible but research and development dollars
have to be allocated. Running the world on Corn
production is not the way to go technologically
even though it satisfies the farming lobby.
March 1st, 2006
A short European
Commision Report on “Food
Quality Sensors” – includes spectroscopy (NMR,
UV/Vis, NIR-Vis, Vis-Fluorescence,
thermoraphy, acoustic impulse, electronic noses).
March 1st, 2006
An excellent
review on the chemistry of cheddar cheese and the
sensory perceptions that arise from that
chemistry. Comprehensive
Reviews in Food Science and Food Safety, Vol 2
(2003).
March 1st, 2006
Low resolution 1H
TD-NMR was utilized to determine the mobility and
translational diffusion coefficients of lipids in
a low moisture (glassy) bread. The mobility of the
lipids was found to be independent of moisture
content. Journal
of Cereal Science (28) 1998, 147-155.
March 1st, 2006
Solid-state 1H and
13C Nuclear Magnetic Resonance (NMR) Spectroscopic
experiments on isolated meteoritic Insoluble
Organic Matter (IOM) obtained from four different
carbonaceous chondrite meteorites; a CR2
(EET92042), a CI1 (Orgueil),
a CM2 (Murchison), and
an undesignated rank 2 meteorite, Tagish Lake. Short
overview web page of NMR
investigations into the carbon chemistry of
meteorites. Journal
article on this subject in PDF
can be found here.If you are interested in
having your meteor materials analyzed by
solid-state 13C NMR
contact John
Edwards at Process
NMR Associates.
February 26th,
2006
February 26th,
2006
Though we have been
performing NMR analysis to
accurately correlate 1H NMR
spectra with physical and chemical properties of
gasoline (distillation, octane numbers, benzene,
aromatics, olefins, oxygenates, RVP,
density) for over a decade, papers still appear in
the literature to vindicate that NMR
is a powerful tool in the gasoline testing arena. In
a Fuel
paper (Vol 83, 2004, 187-193) the Swinss Federal
Laboratories for Materials Testing and Research
demonstrate a integral ratio method was demonstrated
to yield excellent results for many gasoline
parameters of interest to the engineer.
Another strong
proponent of NMR
utilization in the study of petroleum hydrocarbons
is G.S. Kapur of the Indian Oil Corporation. Here
are a few of his papers:
1) “Analysis
of Hydrocarbon mixtures by Diffusion Ordered
Spectroscopy”, Fuel 79, 1347-51 (2000).
2)”The
qualitative probing of hydrogen bond strength by
diffusion-ordered NMR
spectroscopy”, Tetrahedron Letters 41, 7181-7185
(2000).
3)“Unambigous
Resolution of a-Methyl and a- Methylene Protons in
1H-NMR Spectra of Heavy Petroleum Fractions”,
Energy Fuels 2005, 19, 508-511
4)”Simplification
an assignment of proton and 2-dimensional
hetero-correlated NMR
spectra of petroleum fractions using gradient
selected editing pulse sequences” Fuel 81 (2002)
883-892
A practical guide to
PFG
spin echo NMR for mixture
analysis has been written by Brian Antelek of
Eastman Kodak.
February 25th, 2006
An RSC
review paper (Catalysis Volume 17) on the Characterization
of Coke (on catalyst surfaces) is presented at the RSC
site. The review covers use of AES,
IR, Raman, UV, NMR, XRD, SIMS,
etc.
February 25th, 2006
An excellent overview
of NMR applied to porosity
of technology materials is presented in the
dissertation of Roland Valckenborg entitled “NMR
of Porous Technology Materials” (Eindhoven
University of Technology 2001).
Another excellent site covering a peculiar NMR
application to porosity is the site for NMR
Cryoporometry. In this one measures pore
size distribution by freezing liquids in the pores and
then monitoring melting temperatures by NMR
- as the melting point is depressed for
crystals of small size the melting point depression
gives a measurement of the pore simension that the
frozen liquid was in. This is a speciality of Dr.
J.B.W. Webber at the University of Kent, UK.
February 23rd, 2006
Where NMR
will make an impact in the process monitroing arena is
in reaction monitoring where it has huge advantages over
optical spectrocopy due to the chemical resolution
inherent in the spectrum. An excellent poster by Mailwald
et al. presents flow NMR
applied to reaction monitoring utilizing a
superconducting NMR
spectrometer.
February 23rd, 2006
Professor Larry
Bretthorst (Washington University at St Louis) has made
available a Varian
VNMR based software package
for Bayesian analysis of NMR
data. He also maintains a site
on Bayesian probability theory.
February 18th, 2006
Silicon-29 NMR
has a unique ability to probe the detailed solid state
chemistry of silicone rubber materials. The chemical shift
range of the various silicone chemistry groups spans 120
ppm (at 4.9T this equates to 4800 Hz). This is a large
dispersion which allows all chemistry types to be readily
observed. In these, studies, however, we have not
attempted to identify every chemical type present. We have
identified general chemical types and followed their
relative concentration from one sample to the next. Both
cross polarization and single pulse experiments were
performed on magic angle spinning samples (a full
explanation of these two complimentary experiments is
given below). Optimal experimental conditions were
initially obtained and all subsequent samples have been
analyzed under identical conditions to facilitate an
understanding of the spectral changes from a chemistry as
well as molecular mobility standpoint. Set NMR
experiment conditions were used because of the time
consuming nature of these experiments which typically take
around 12 hours for each of the cross polarization and
single pulse experiments.
Experimental
At the present time samples are being run on a Varian
UnityPlus-200 spectrometer operating at a 29Si frequency
of 39.74 MHz. The probe was a Doty Scientific 7 mm
Supersonic CP/MAS probe using zirconia and Kel-F end caps.
For the single pulse NMR
experiments a pi/6 pulse of 2 microseconds was used with a
relaxation delay of 4 seconds to facilitate quicker
acquisition.The 4 second relaxation delay was obatined
from full T1-inversion recovery experiments. Gated proton
decoupling was used during FID
acquisition. For the cross polarization experiments full
contact time array experiments were obtained on the
initial samples submitted. Due to the mobility of the
polymer backbone the optimum cross polarization contact
time for the polymer backbone was around 15 ms with signal
lasting until 50+ ms. However, the more rigid structures
in the polymer – such as the silicates, had optimum
contact times around 3-5 ms. As a compromise we chose a
6.4 ms contact time which yielded good signal sensitivity
for both the polymer and silicate components. Cross
polarization inversion recovery experiments yielded a
short relaxation delay of 2 seconds. A
1H p/2 pulse of 4.6 ms was used along with gated
proton decouplind during FID
acquisition. For all samples the same experimental
conditions have been maintained. MAS
spinning speeds were around 7 kHz to avoid spinning side
band coincidence on real signals. Also, to avoid MAS
induced modulation of the contact-time, the variable
amplitude cross-polarization contact pulse was used.
Silicone Chemistry
Observed by NMR
The notation in use for silicone chemistry is M,D,T,Q
(mono, di, tri and quaternary) denoting the oxygen
substitution on the silicon atom. The polymer backbone
itself is predominantly D i.e. [(SiO2(CH3)2]n which has a
typical resonance frequency around –21 ppm. The
termination of the polymer would be an M group (SiO(CH3)3)
(found at +4 to +10 ppm) or MOH (SiO(CH3)2OH)
(-10 to –15 ppm). Another area of interest in the
spectrum is the –20 to –10 ppm region which is
partially due to MOH but also
due to D type silicon centers that are within 5 monomer
units of a termination. Thus, if hydrolysis of the
silicone backbone is occuring, this region will increase
in intensity as one will now have more silicon centers
close to termination points as well as more MOH
terminations.
In some gaskets one
observes small signals in the –60 to –70 ppm region
which is due to T type silicone centers (SiO3(CH3))n,
however this is usually not observed. The only other
region where one observes signal is in the –80 to –120
ppm region of the spectrum. These silicon centers can only
be Q1 (SiO(OH)3), Q2
(SiO2(OH)2), Q3 (Si(OSi)3(OH))
or Q4 (SiO4)types, as only
silicons with 4 attached oxygens can appear in this
region, any methyl substitution would cause these silicons
to appear in the +10 to –70 ppm range of the spectrum.
Of relevance to any discussions on silicone polymers it
should be noted that Q1 is equivalent to M(OH)3 , Q2 is
equivalent to D(OH)2 , Q3 is equivalent to TOH.
When one looks at the NMR
experiments for the certain silicones one does not observe
a resonance at +10 to +4 ppm. This indicates that the
predominant polymer termination is MOH.
Silicate is observed, however, it is not clear if this
silicate is a filler for hydrogen bonding crosslinking or
actual polymer Q4/Q3/Q2 sites of directly condensed
silicates acting as bonded crosslinking agents.
SP-MAS NMR
Experiments
In this experiment one quantitatively observes all silicon
species in the system allowing a “bulk” silicon type
distribution to be calculated. One observes a narrow
resonance at –21 ppm which is due to the silicone
polymer backbone (-O-Si(CH3)2-O-)n. Very little signal is
observed in the –20 to –10 ppm region indicating that
the polymer chains are quite long. In the –80 to –120
ppm region of the spectrum one observes silicon present in
silicate that has been added as a cross-linking agent. The
hydrogen bonding between the silicone polymer and the Si-OH
groups of the silicate add structural integrity to the
gasket. It is differences in the silicate silanol (Si-OH)
chemistry that may account for changes in compressibility
of the gasket during service. Thus, one will observe
relative changes in the amount of 29Si signal observed in
the –80 to –103 ppm and –10 to –23 ppm regions of
the spectrum. This region is where Q3 (Si(OSi)3(OH)),
Q2 (Si(OSi)2(OH)2), and Q1
(Si(OSi)(OH)3) groups are found.
Parameters
Calculated:
Silicate Content - %Si in silicate filler
Q4
- %Si atoms in Q4 silicate – Si(OSi)4
Qn
- %Si atoms in Qn silicate (Q1, Q2, Q3)
Q4/Qn Ratio - Silanol
(Si-OH) distribution
%
Polymer
- %Si in D & MOH polymer
units
Relative changes in these
parameters can be utilized to interpret changes in silicon
chemistry caused by coolant exposure and service.
CP-MAS NMR
Experiments
This experiment warrants a detailed explanation as the
results are not quantitative from a “bulk” silicon
chemistry standpoint. The CPMAS
experiment utilizes the strong NMR
signal that can be generated from protons (H) in the
sample. The experiment preferentially observes silicons
that are in close proximity to H. However, mobility is
also a “problem” in this experiment. The way the
experiment works is that the protons in the sample are
polarized initially and magnetization is transferred from
the protons to the silicons via their dipole-dipole
interaction (similar to the interaction between 2 bar
magnets). This interaction weakens the further the H and
Si are from each other, and also weakens if there is
considerable molecular motion. In the case of these
samples this means that in the silicate region of the
spectrum one observes an enhancement of the signal due to
Si-OH containing species. In the case of the silicone
polymer, however, one observes an overall decrease in the
signal at –21 ppm due to the –(O-Si(CH3)2-O-)n
backbone due to its rapid segmental (rubbery) molecular
motions. One observes a large signal (that is hardly
observable in the SPMAS spectra)
in the –5 to –20 ppm region. This is due to silicone
silicons that are at or directly adjacent to crosslinking
sites (where there could be a D-silicate bond, or polymer
termination sites such as MOH.
The fact that they are enhanced by the CP technique
indicates that these termination proximate silicons are
motionally restricted compared to the rest of the silicone
backbone. They represent either strongly hydrogen-bonded
regions or chemical crosslinks of the type
(O2(CH3)2Si–O–Si-O–Silicate) where a defect in the
silicone backbone has reacted with a silanol of the
silicate filler to form a Si-O-Si bond. This experiment is
very powerful when used to observe relative changes in Si-OH
chemistry in the silicate region and relative mobility
changes in the polymer backbone.
Parameters
Calculated:
% polymer
backbone
- %Si in mobile silicone backbone
% restricted polymer backbone - %Si in motionally
restricted regions of the silicone backbone (D units in
close proximity to cross-linking sites, termination sites
(MOH) or adjacent to termination sites).
Silicate
Content
- %Si in silicate filler.
Q4
- %Si in Q4 silicate – Si(Osi)4
Qn
- %Si in Qn silicate (Q1, Q2, Q3)
Q4/Qn
Ratio
- relative change in silanol (Si-OH) distribution
As with the SP-MAS
calculated parameters one can utilize these parameters to
determine changes in silicon chemistry resulting from
coolant exposure and service.
Table I
Summary of 29Si NMR Chemical
Shift Regions
Chemical Shift
Region (ppm)
Silicon Species
+10 to
+4
Polymer termination sites (SiO(CH3)3) M
-5 to
–15
Polymer Termination Sites (SiO(CH3)2OH) MOH
-10 to
-20
Motionally restricted silicone polymer. Cross-linked and
H-bonded –(O-Si(CH3)2-O-)n D units within five monomer
units of polymer termination
-21
D Units – motionally unrestricted silicone
–(O-Si(CH3)2-O-)n
-75 to
-85
Q1 Si(OSi)(OH)3 Silicate Center
(M(OH)3)
-85 to
-94
Q2 Si(OSi)2(OH)2 Silicate Center
(D(OH)2)
-94 to
-104 Q3
Si(OSi)3(OH) Silicate Center (TOH)
-104 to
-120 Q4 Si(OSi)4
Silicate Center (Q)
Discussion
In use one observes that the gasket silicon chemistry
changes dependent on additive chemistry and
temperature/pressure conditions. When the polymers degrade
one observes a general loss of D type signal intensity in
the 29Si SP/MAS experiment as well as a corresponding
increase in silicate content. One does not typically see
changes in Q4 type but instead large changes in Q3 and Q2
content. These changes occur regardless of the presence of
silicate in the coolant. This leads one to deduce that the
Q3 and Q2 types are being generated by degradation of the
polymer itself rather than a change in the chemistry of
the silicate that was present in the sample initially. The
author is not privy to additives and experimental
conditions so he cannot speculate on the effect of
silicate and other additives on the speed of the
degradation that occurs. At the same time that Q3 and Q2
types are increasing in intensity the CP/MAS experiment
clearly shows that there is a large increase in the
relative amount MOH types and D
types close to terminations (-5 to –20 ppm region). This
proves that the exposure to coolants causes a hydrolysis
of the Si-O-Si bond. However, it should also be notes that
for the Q3 and Q2 types to appear one must also be
hydrolyzing the Si-CH3 bonds.
The complimentary nature
of the SP/MAS and CP/MAS experiments along with the use of
only on set of experimental CP/MAS conditions means that
relative changes in the various silicon chemistries can be
analyzed to quantify the degree of degradation that a
polymer has gone through.
Excellent Silicone
Chemistry Link – Silicones
in Pharmacutical Applications
For more information on this topic please contact:
John
Edwards
Manager, Process and Analytical NMR Services
Process NMR Associates LLC,
87A Sand Pit Rd
Danbury, CT 06810, USA
Tel: (203) 744-5905
February 16th, 2006
“High
Temperature Simulated Distillation” by Dan Villalanti
et al. in Encyclopedia of Analytical Chemistry, “Yield
Correlations between Crude Assay Distillation and High
Temperature Simulated Distillation” by Villalanti et
al., and “Refinery
Analytical Techniques Optimize Unit Performance” . All
discuss the panacea of developing rapid HTSD
as a suitable replacement for the very lengthy crude assay
distillation.
February 15th, 2006
Residue
Upgrading Technologies are discussed in severla papers
including one
presented in India, and another at ERTC
2004 in Prague In Moscow at the 1st Bottom of the
Barrel Technology Conference a paper was presented on “Delivering
Value for Resid and Heavy Feed“.
February 15th, 2006
Oil exploration companies
are using NMR measurements in a
number of downhole applications, such as characterizing
formation fluids during reservoir evaluation and assessing
formation producibility. In their article “Trends
in NMR Logging” Schlumberger
describe how NMR technology is
changing the way reservoirs are designed, developed and
managed. A similar paper, “Advances
in NMR Logging” is presented
by Robert freedman of Schlumberger.
Another review
was produced in 1995, and “How
to Use Borehole Nuclear Magnetic Resonance” was
produced in 1997.
NMR
Petrophysics offers NMR
logging courses and provide NMR
log analysis services.
A paper on the
effect of sorbed oil on 1H NMR
response was published byStanford University
researchers.
A book is available on the
subject entitled, “NMR
Logging – Principles and Applications”
“Oil-Viscosity
Predictions From Low-Field NMR Measurements”
by J. Bryan and A. Kantzas, U. of Calgary/Tomographic
Imaging and Porous Media Laboratory, and C. Bellehumeur, U.
of Calgary
February 15th, 2006
Practical
Applications of NMR in Civil
Engineering by Bernd Wolter, Frédéric Kohl, Nina
Surkowa, Gerd Dobmann
Fraunhofer-Institut fuer zerstoerungsfreie Pruefverfahren (IZFP),
Saarbruecken, Germany
February 15th, 2006
A neew book on Emerging
Technologies for Food Processing has been published by
Elsevier, edited by professor Da-Wen Sun ( National
University of Ireland, Dublin) and has contribution from KVL
Quality & Technology: Monitoring
Thermal Processes by NMR Technology
by Nanna Viereck, Marianne Dyrby and Søren B. Engelsen.
(Oct 2005)
February 15th, 2006
Professor
Alexej Jerschow has made available a Mathematica package
that allows calculation of spin and spatial tensors – it
is available at the following link : MathNMR.
Also available at this site
are a very handy palm utility that lists frequencies,
gyromagnetic ratios, natural abundances, receptivities,
magnetic and quadrupolar moments, and reference compounds of
most NMR active nuclei –
download PalmNMR.
He also provides a nicely designed interactive
NMR frequency map.
February 15th, 2006
Stanislav Sykora, in his NMR
blog describes a recent patent applied for by himself
and Paola Fantazzini, under the auspices of the University
of Bologna. The patent surrounds a new pulse sequence that
will allow selective excitation of components of a complex
mixture based on the T1 relaxation differences between the NMR
active nuclei in the components. The pulse sequence
pre-amble is called PERFIDI. The
Italian patent (#BO2005A000445 of July 01, 2005) is
currently confidential but the invcentors have set up a website
for potential licensors of the technology. The website
includes a brief overview of the patent.
February 15th, 2006
February 13th, 2006
Ken Skidmore at San Francisco State University has finally answered the question on our lips for about a decade now….can NMR
do the dew? Seems that it can, in an incredible turn of events the
syrup formula has finally been exposed for what it really is… a $%!*
load of sugar – the NMR evidence is irrefutable.
February 9th, 2006
BioNMR is a forum for NMR spectroscopists to discuss their projects and find help from the online NMR community.
An excellent NMR users group exists (AMMRL-Association of Managers in Magnetic Resonance Laboratories) which consists of NMR facility managers and industrial NMR users. The group has an archive of questions posed and answers given to many issues that arise from the operation of Varian, Bruker and JEOL spectrometers predominantly in a college setting. Issues with NMR
operation such as safety and peripheral infrastructure, as well as
scheduling of users, manipulation of data and servicing of equipment
are all covered in the discussions. Both groups can be joined at the
sites above.
There is a Bruker users group archive directory located at http://calmarc3.cchem.berkeley.edu/archives/bum/. Membership of the Bruker users group can be obtaied by contacting he following e-mail (‘bruker-users-mail-request@purcell.cchem.berkeley.edu’). Membership to the Bruker brotherhood is carefully guarded and you will only be admitted if you operate Bruker equipment.
February 9th, 2006
Dr. Kirk Marat at University of Manitoba has developed (and continues to develop) and excellent NMR processing freeware package that works very intuitively and well.
The FTP link to download the software is:
ftp://davinci.chem.umanitoba.ca/pub/marat/SpinWorks/.
The current version is 2.5.3. There is also an excellent documentation PDF file to help users work through the program functionality.
This is how Dr Marat describes his software on his home page:
“What is SpinWorks
SpinWorks has two functions: The first is to provide easy basic off-line processing of 1D NMR
and 2D data on personal computers. SpinWorks other function is the
simulation and iterative analysis of complex second order spectra
including dynamic NMR problems and certain solid-state NMR problems, in a manner similar to our UNIX Xsim
program. SpinWorks 2.4 is the forth release of SpinWorks version to
contain 2D processing. Full support is included for Bruker
(XwinNMR/UXNMR) and Varian (Unix VNMR) data formats. Included F1 detection modes include States, TPPI,
States-TPPI, Single Detection (QF), and echo-antiecho. There have also
been some improvements and bug fixes in the 1D and simulation routines,
and these should be at least as stable as those in version 1.3. While
the program is to the point where it should (I hope) be useful, there
will, no doubt, be bugs and there are things that don’t yet work. The
aim of the program is to make a program easy enough for undergrads to
process magnitude COSY spectra (for example)
with a single mouse click, and yet still be flexible enough for
research use. SpinWorks currently handles only one data set at a time.
However, most new computers have sufficient memory to run two or three
copies of SpinWorks simultaneously. This can be very useful when
examining the rows and columns of a 2D data set.
Computer Requirements
SpinWorks requires a 486 or higher processor (Pentium recommended) running Windows 95, 98, NT 4.0, Windows 2000 Pro, or XP (NT
4.0, XP or Win 2000 recommended). Windows ME is probably O.K., but is
untested. Installation currently requires about 5 Mbytes of disk space
exclusive of NMR data. 32 Mbytes or more of RAM are recommended, depending on NMR data set and simulation sizes. SVGA 800
x 600 or better display required (1024×768 or better recommended). For
2D processing a Pentium class processor with 64 Mbytes of memory is the
practical minimum. For 2D you should also have your display set to at
least 16 bit colour, otherwise the image and contour level colours will
be strange. I have received reports (but have not confirmed) that
SpinWorks will run under Linux with the WINE
package and on a Mac with SoftWindows. A three-button mouse is ideal,
but SpinWorks will work just fine with a two-button mouse. Note that on
“Wheel Mice” the mouse wheel also serves as the middle mouse button.
The mouse wheel can also be used for vertical scaling of 1D spectra.”
February 8th, 2006
High field 1H and 13C NMR
has been used to identify the region where an olive oil was produced –
See Segre et al.
Other methodologies have involved reacting hydroxyl groups in the olive
oil with phospochloridite which allows detailed 31P NMR
signatures to be obtained that reveal detailed chemistry distributions
within the olive oil allowing an even greater discernment of chemical
differences based on origin. Much of the work in this area has been
performed by Apostolos Spyros in Crete. Here are a few of his papers:
“Application of 31P-NMR
spectroscopy in food analysis. I. Quantitative determination of mono- and
diglycerides in virgin olive oils”. A. Spyros, Photis Dais, J. Agric.
Food Chem., 2000, 48, 802 . (pdf)
“Quantitative determination of
the distribution of free hydroxylic and carboxylic groups in unsaturated
polyester and alkyd resins by 31P NMR
spectroscopy”.A. Spyros, J. Appl. Polym. Sci., 2002, 83, 1635. (pdf)
“Kinetics of diglyceride formation and isomerization in virgin olive
oils by employing 31P NMR spectroscopy.
Formulation of a quantitative measure to assess olive oil storage
history”. A. Spyros, A. Fillipidis and P. Dais, J. Agric. Food Chem.,
2004, 52, 157. (pdf)
This approach has also been
applied to other edible oils so that their presence as adulterants can be
observed and quantified:
“Classification of edible oils
by employing 31P and 1H NMR Spectroscopy in
combination with multivariate statistical analysis. A proposal for the
detection of seed oil adulteration in virgin olive oils “. G. Vigli, A.
Fillipidis, A. Spyros and P. Dais, J. Agric. Food Chem., 2003, 51, 5715. (pdf)
“Detection of extra virgin olive oil adulteration with lampante olive
oil and refined olive oil using NMR spectroscopy
and multivariate statistical analysis”. G. Fragaki, A. Spyros, G.
Siragakis, E. Salivaras, P. Dais, J. Agric. Food. Chem., 2005, 53, 2810.(pdf)
Please contact Process
NMR Associates with your potential 31P
analysis.
February 8th, 2006
Magnetic resonance sniffs out bad
wine
Physics in Action: November 1998, Claude Guillou and Fabiano Reniero
Nuclear magnetic resonance (NMR)
has come a long way since it was discovered in the 1940s. This physical
phenomenon, which arises from the intrinsic spin possessed by many nuclei,
has provided a better understanding of the physics of nuclei and
molecules. It has also been exploited to analyse the properties of many
different materials in chemistry, physics, polymer science and
biomedicine.
Recent developments in the use of
high magnetic fields and pulsed NMR techniques
have made it possible to probe the structure of organic compounds as
complex as proteins. Imaging machines based on the NMR
principle have also been developed, and now provide a powerful and
non-invasive tool for diagnosing a variety of medical conditions. However,
less well known are the applications of NMR for
analysing food and drink. At the Joint Research Centre at Ispra, we are
using a technique to detect whether a wine has been adulterated with
foreign substances. This method is based on an NMR
measurement of the deuterium content of wine.
Nuclear magnetic resonance is
observed for nuclei with non-zero nuclear spin, which includes both the
hydrogen nucleus (a proton) and the deuterium nucleus (a proton and a
neutron). However, the physical properties of these two isotopes dictate
that the NMR signal produced by deuterium nuclei
is over 100 times weaker than that produced by the same number of hydrogen
nuclei. The natural abundance of deuterium is also extremely low, with
typical samples of hydrogen containing only about 0.015% of deuterium.
This means that the NMR signal due to deuterium
in a natural sample containing hydrogen is about a million times weaker
than the signal due to hydrogen.
Despite this drawback, deuterium
has very interesting properties for quantitative NMR.
Deuterium has a quadrupole magnetic moment rather than a dipole moment,
which means that it is unaffected by the nuclear Overhauser effect. This
effect – in which radiofrequency radiation applied to the nucleus
changes the strength of the resonance – is often exploited to enhance
the NMR signal, but it also degrades the
precision of quantitative techniques. Indeed, deuterium spectra generally
show distinct peaks that are suitable for quantitative purposes.
An important advantage of NMR
is that the deuterium content can be determined for each of the sites in a
hydrogen-containing molecule that are not magnetically equivalent. For
ethanol, for example, it is possible to determine separately the deuterium
content of the methyl group (CH2D) and the methylene alcohol group (CHD)
in the deuterium NMR spectrum. The low natural
abundance of deuterium means that it is only necessary to consider
molecules containing a single deuterium atom.
How does the deuterium content of
wine indicate whether it has been adulterated? This is possible because
the deuterium content of water in the hydrosphere and biosphere is not a
constant. As an extreme example, ice at the South Pole has very low
deuterium content, with a deuterium-to-hydrogen ratio of about 90 parts
per million (ppm), while ocean water has a value of about 156 ppm. This
natural variation is due to thermodynamic and kinetic effects that take
place during the water cycle, when water evaporates from the ocean and
precipitates over land. The transpiration of water from plants also
favours lighter isotopes, leading to a greater abundance of deuterium in
the water contained in plants.
The deuterium content of the
water in any plant, including the vines used in wine production, therefore
depends on several factors that can be related to the geoclimatic
conditions during plant growth. Moreover, the water in the plant is used
in the photosynthesis of different chemicals, in particular the production
of glucose. This transfers the isotopic content of the water to the
glucose and other sugars present in the plant, which means that both the
metabolism and physiology of the plant influence the final deuterium
content of the sugars. The deuterium content of the sugars therefore
provides a good indication of their botanical origin.
Although sugars are particularly
difficult to study with deuterium NMR, it is
possible to detect the deuterium content of the methyl group in ethanol,
which is produced during the yeast fermentation of wine. Ethanol is
responsible for most of the alcoholic content of wine, and it retains a
deuterium-to-hydrogen ratio representative of the sugars from which it is
produced. Quantitative NMR can therefore be used
to determine whether the ethanol present in wine originates from the
sugars naturally present in the grapes or whether other sugars have been
added to boost the alcoholic content. This practice – known in the trade
as “chaptalization” – is allowed in the European Union, but only
within specified limits.
A simple way of using NMR
to detect sugar in wine is to compare the deuterium content of the wine
being tested with a genuine wine from the same geographical origin. This
requires an accurate determination of the NMR
signal from the genuine wine, which is being done for all European
wine-producing countries by our laboratory and other official laboratories
of the European Union. The NMR data of more than
10 000 samples, together with an exhaustive description of the wines, have
been collated since 1991 and now provide a powerful tool against
fraudulent practice.
Other isotopic indicators, such
as the content of oxygen-18 in wine or carbon-13 in ethanol, can be used
to help detect other types of fraud, such as watering down the wine or
false declarations of geographic origin. These parameters are usually
measured by mass spectrometry, but this does not provide the site-specific
information given by deuterium NMR.
Isotopic techniques, particularly
the NMR analysis of deuterium, can also be used
to control the authenticity of fruit juices by first converting the sugars
into ethanol using controlled fermentation. Deuterium NMR
can also be used to characterize the origin of natural flavours such as
vanillin or raspberry. In future the combination of nuclear magnetic
resonance and mass spectrometry will almost certainly lead to many other
applications in detecting frauds in food.
About the author
Claude Guillou and Fabiano Reniero are at the Joint Research Centre of the
European Commission, Ispra, Italy.
February 8th, 2006
Bristol-Myers Squibb researchers
have patented a methodology to determine the presence of particular
molecular substructures in compounds by PCA
analysis of NMR spectroscopy data. This analysis
is performed on entire spectra or particular regions defined by the
substructures of interest. US
Patent 6,895,340
February 8th, 2006
Ex-situ NMR (US
Patent 6,652,833) is currently available for license from the Lawrence
Berkely Lab. This NMR analysis is described in
a paper presented in Physique
and in the following Science article (“High-Resolution NMR
Spectroscopy with a Portable Single-Sided Sensor” by J. Perlo, V.
Demas, F. Casanova, C. A. Meriles, J. Reimer, A. Pines, and B. Blumich
(2005). Science 308: 1279-1279
February 8th, 2006
A large bore superconducting magnet
and specialized probe is all that is required to check that your $4500
bottle of Mouton Rothschild 1865 is not a extraordinarily expensive bottle
of vinegar US
Patent 6,911,822.
February 8th, 2006
Pattern recognition technology in
conjunction with 1H and 13C NMR spectroscopy is
used to determine the standard specification expected for medicinal grade
natural products – see US
Patent 6,806,090
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