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You are here: Home / Archives for NMR

Solid-State 13C NMR Analysis of Herbal Supplements

November 27, 2010 by process nmr NMR

Solid-state 13C NMR is an excellent way to investigate what chemical functionality is present in herbal supplements. The large resonances at 60-105 ppm are due to cellulose/polysaccharides and some sugars. The peaks in the 0-60 ppm region are aliphatic carbons in fatty acid chains. Peaks in the 110-140 ppm region are alkene and aromatic carbons, while peaks in the 140 ppm and 150 ppm region are due to substituted aromatics and phenolic carbons. Peaks in the 160-200 ppm region are due to carboxylic acids, esters and amides. Solid-state NMR is a relatively simple technique that involves no sample preparation and observes the sample carbon chemistry in it’s entirety. The analysis reveals relative amounts of chemical functionality that can be utilized for product-to-product comparison or batch-to-batch manufacturing comparison. The chemical specificity of the technique also means that adulterants can readily be detected and identified. A few examples of “off the shelf” herbal supplements are shown below.

Solids 13C NMR of Green Tea - Cranberry - Milk Thistle

Figure 1: 13C CP-MAS NMR of Cranberry Extract, Green Tea Extract, and Milk Thistle Extract

Solids 13C NMR - Bilberry - Echinecea - Black Cohosh

Figure 2: 13C CP-MAS NMR of Black Cohosh Root Extract, Echinecea Powder, and Bilberry Extract

13C NMR of Valerian Ginseng Saw Palmetto, St Johns Wort

Figure 3: 13C CP-MAS NMR of Valerian Root Extract, Ginseng Extract, Saw Palmetto Extract, Grape Seed, and St John’s Wort.

For further details on these analyses and their utilization in quality control contact John Edwards

Benchtop Permanent Magnet High Resolution NMR Systems

November 24, 2010 by process nmr NMR, Process NMR

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

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

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

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

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

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

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

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

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

Press Release: IASC Chooses Process NMR Associates to Provide Analytical Services for Certification Program

November 24, 2010 by process nmr Herbal Supplement, NMR Tagged: Aloe Vera, IASC, NMR Test

The International Aloe Science Council (IASC), a trade association representing the global aloe vera industry, has selected Process NMR Associates, LLC (PNA) as its primary provider for Nuclear Magnetic Resonance (NMR) spectroscopic measurement of aloe vera in regards to the organizations seal-based certification program. PNA’s services include measurement of aloe vera concentration, sacharride distributions, formulation ingredients, and, contaminant/degradation products, in aloe vera powders, whole leaf extracts, whole leaf and inner leaf gel concentrates, drink concentrates, and, ready to drink
formulations.

The IASC certification program, which offers manufacturers the ability to place a seal on products demonstrating that it meets the established standards for quality and purity of aloe vera products available in the marketplace, has elected to use quantitative 1H NMR analysis as a means to determine compliance. “We are pleased to partner with Process-NMR Associates for providing analytical services related to the certification program,” said Devon Powell, Executive Director of the IASC. “PNA has demonstrated its capability to provide excellent analytical services in a timely manner to the organization and aloe vera
industry at-large.”

PNA performs the NMR methodology prescribed by IASC, quantifying constituents such as acemannan, and glucose, identifying breakdown products such as acetic acid, lactic acid, pyruvic and succinic acid, and verifying formulation/preservative additives such as citric and benzoic acids. Adulterants such as maltodextrin can be readily quantified and the presence of non-aloe vera products can also be determined.“Process NMR Associates is proud to have been chosen as a partner for IASC’s certification program needs,” said John Edwards, PNA Manager. “Our commitment to quality analytical services, sample analysis, reporting turnaround, and competitive pricing enable us to provide value-added services to IASC
and others in the aloe vera marketplace.”

The International Aloe Science Council (IASC) is the global trade association dedicated to serving the needs of the aloe vera industry, with a mission to advance, promote and represent the aloe vera industry by providing educational, scientific and self-regulatory leadership and guidance. Membership information can be found at www.iasc.org. Contact: Devon Powell, Executive Director 301.588.2420 x102 (dpowell@iasc.org)

Established in 1997 PNA is a process analytical consulting company and analytical testing laboratory with over 45 years of experience in the field of nuclear magnetic resonance spectroscopy (“NMR”) and organic spectroscopy (FTIR, NIR, ESR). PNA operates high field analytical NMR laboratory for liquid and solid state multinuclear and multi-dimensional NMR analyses. PNA also has several permanent magnet NMR systems that are utilized for laboratory, at-line, and, process FT-NMR and TD-NMR applications. The lab also includes an ATR-FTIR spectrometer, a micro-ESR spectrometer and a Simulated Distillation Gas Chromatograph. Consultation services for analytical technology and application development, development of new instrument platforms and integrate NMR technology with other analytical techniques are also provided. (www.process-nmr.com) Contact: John C. Edwards, Manager, Analytical and Process NMR (john@process-nmr.com)

Process NMR Associates to Present at 3 Meetings

May 5, 2010 by process nmr NMR

I will be presenting a poster and two invited talks at three meetings this Summer and Fall. The first meeting is Petrophase XI 2010 (11th International Conference on Petroleum Phase Behaviour and Fouling) in Jersey City, NJ, June 13-17 – my poster is entitled: “Improved Approach to the Calculation of Average Molecular Descriptions of Heavy Petroleum Hydrocarbons by Combined Analysis by Quantitative 13C and DEPT-45 NMR Experiments”. The poster describes a new methodology for 13C NMR analysis of heavy petroleum materials based on quantitative 13C and DEPT experiments which can be used in combination to calculate an average aromatic cluster size that is consistent with other analysis techniques. Published approaches being used currently underestimate the size of the aromatic groups in heavy petroleum materials.

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

I will be presenting an invited talk in a session on reaction monitoring with NMR at SMASH 2010 in Portland Oregon, September 26-29 – my talk is entitled: “Simple and Continuous Flow Reaction Monitoring by High Resolution Bench-top Permanent Magnet 1H NMR at 60 MHz”, by John C. Edwards, Paul J. Giammatteo, at SMASH 2010, in Portland, Oregon.

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