Application Notes
Easy to follow examples of the Polyarc system in action:
2017
Quantification of Monomer Concentration without Calibration and Internal Standard using GC/Pyrolysis and the Polyarc Reactor
Author(s): Cidnie Hoang, BEHR Process Corporation
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A Polyarc system was used, in conjunction with the traditional GC-Pyro/FID technique, for monomer concentration quantification. As with any chromatography method, monomer concentration quantification also requires multiple point calibration for each of the monomer of interest. With the Polyarc, the concentrations of BA and MMA monomers in an in-house prepared mixture were successfully quantified with relative errors of 3.6% and 3.2%, respectively. This was done with neither calibration nor the use of an internal standard. The results for BA and MMA in the 100% acrylic copolymer binder sample were also highly accurate, with relative errors of 0.9% and 1.5% for BA and 0.6% and 1.2% for MMA, with and without EGDE (internal standard), respectively. These show that no calibration or internal standard are required for monomer concentration quantification in a copolymer mixture.
Equimolar and Linear Carbon Response over 7 Orders of Magnitude for Alcohols, Ethers and Hydrocarbons
Author(s): Andrew Jones, Activated Research Company
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The conversion of compounds to methane before detection by FID improves signal response and linearity over 7 orders of magnitude. The normalized response increases proportionally with the amount of carbon injected with a proportionality constant of one. The uniform detector response can lead to improved data integrity and simplified workflow when compared with other common detector technologies. A reduction in calibration can lead to time savings of over 58% with increased accuracy.
Accurate Fragrance Duplication with a Single Injection using the Polyarc System
Author(s): Joe Nuckolls, Chemia Corporation Fragrance and Flavor; Charlie Spanjers, Activated Research Company
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A complex test mixture containing 21 fragrance components was analyzed with the Polyarc system. In a blind study, the Polyarc was shown to provide accurate fragrance component concentrations with a single injection and without the need for calibration of the system. The method using the Polyarc was more accurate than an uncalibrated GC/MS method for 20 out of 21 of the components.
Saving Time by Reducing Calibrations for the Quantification of VOCs in Paints and Coatings using the Polyarc System
Author(s): Nemi Jain and Evelyn Rouge, Sherwin-Williams Co.; Charlie Spanjers, Activated Research Company
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The analysis of volatile organic compounds (VOCs) in solvent-borne as well as waterborne paints and coatings by GC/FID typically requires calibrations to determine the responses of each individual analyte before quantitative information can be obtained. In this application note, the analysis of a commercial coating with the Polyarc System is demonstrated. Because the Polyarc converts all organic molecules to methane before detection in the FID, calibration is not required. Instead, the peak area of one internal standard is used to accurately quantify every component in the mixture (17 analytes in this example).
Calibration-Free Quantification of Lactic Acid and Lactic Acid Oligomers in Concentrated Aqueous Lactic Acid Solutions Using GC/Polyarc®/FID with Deans Switch
Author(s): Oliver Palardy, NatureWorks LLC; Charlie Spanjers and Andrew Jones, Activated Research Company
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Quantification of compounds for which standards are not commercially available can involve costly synthesis of said compounds, or time-intensive approaches utilizing multiple analytical methods. Such a predicament is encountered when attempting to quantify the different lactic acid oligomers present in aqueous lactic acid solutions of a given total wt% lactic acid. In this application note, a simple, calibration-free method for quantifying lactic acid and its low molecular weight oligomers in an 88 wt% aqueous lactic acid solution is described. The data obtained with this method is compared with data obtained using other analytical methods.
Sub 1 mg/kg (1 ppm) Detection of Carbon Disulfide with the Polyarc® System
Author(s): Charlie Spanjers, Activated Research Company
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The analysis of low levels of carbon disulfide (CS2) is important in the pharmaceutical, food, environmental, and other industries, but there exist few simple, low-cost, methods for analysis because the ubiquitous flame ionization detector (FID) is insensitive to CS2. Here, the Polyarc System (i.e., Polyarc/FID) is shown to be a low-cost solution for low-level analyses of carbon disulfide down to a minimum detection limit of 0.14 mg/kg (0.14 ppm).
Quantification of Tentatively Identified Extractables and Leachables with Mass Spectrometry and Polyarc®/FID
Author(s): Jianxin Yu, Ashley Baeten, and Scott Citrowske, Abbott Laboratories
Note – This application note describes the analysis of non-derivatized acids with the Polyarc. Free acids can adsorb/degrade during GC analysis, and thus some Polyarc RRFs may be non-uniform as complete sample transfer to the detector may not have been obtained in this application note.
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Extractable and Leachable (E&L) evaluations have become increasingly more vital to successful medical device product development and regulatory submissions. According to requirements and guidance from the US Food and Drug Administration (FDA), European Medicines Agency (EMA), ISO and the Product Quality Research Institute (PQRI)[1-4], E&L profiles should be established by exhaustive extraction with multiple solvents of varying polarities and reliable determination with distinctive analytical techniques.
Gas chromatography mass spectrometry (GC-MS) analysis with headspace (HS) or liquid injection detects volatile and semi volatile components in E&L studies. Due to the complexity of materials and the unpredictability of an E&L analysis, two-step analysis (initial screening and target analysis) is usually employed for qualification and quantification of compounds detected. This is a costly, time consuming and labor-intensive process.
The Polyarc®/FID system converts carbon atoms of organic molecules found in the column effluent into methane which then generates an FID response. The resulting detector response is uniform on a per carbon basis and allows the FID to have a truly universal carbon sensitivity. This eliminates the need for calibration standards for each identified compound to determine an internal or external standard’s response factor. Gas chromatography using full scan MS combined with parallel Polyarc®/FID detection could apply to E&L studies, integrating a two-step process into a one-step analysis.
Two XTI -5MS Columns were installed into the front inlet of a 6890 GCMS. One of the columns was connected to the 5975 Mass Spectrometer while the other was connected to the Polyarc® and FID. Two groups of known extractables and leachables of concern were prepared in acetone solutions at concentrations ranging from 50 µg/mL to 100 µg/mL. These preparations were spiked with a known volume of internal standard at a concentration of 25 µg/mL before triplicate analysis on the instrument. Calculation of the relative response factors of each analyte was performed with both the Mass Spectrometer and Polyarc®/FID data for comparison.
Quantification of Compounds with Low or Negligible Response in Traditional FID using the Polyarc® Reactor
Author(s): Paul Dauenhauer and Connor Beach, University of Minnesota; Charlie Spanjers and Andrew Jones, Activated Research Company
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The flame ionization detector (FID) is widely used in the field of gas chromatography because it is highly sensitive to many organic compounds and provides a linear response over many orders of magnitude. However, FIDs suffer from two main drawbacks: the response to analytes are variable (and therefore require time-consuming calibration) and the FID provides low or no response to highly functionalized molecules such as carbon monoxide, carbon dioxide, formic acid, formaldehyde, and formamide. In this application note, we show that an FID equipped with a Polyarc reactor is not only highly sensitive to these compounds but also provides a response factor that is equivalent for all carbon-containing compounds, thus eliminating the need for time-consuming calibration. Compared to conventional FID-only systems, the Polyarc reactor eliminates the need for a second detector to quantify carbon monoxide and carbon dioxide, improves accuracy in quantitative analysis, and saves time and money associated with calibrations.
Simultaneous Compound Identification and Quantification with Parallel Polyarc®/FID and MS
Author(s): Erick White, National Renewable Energy Laboratory; Charlie Spanjers and Andrew Jones, Activated Research Company
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Quantification of unknowns with gas chromatography traditionally requires time-consuming and costly calibration steps including purchasing, preparing, and analyzing calibration standards, and applying the calibration results to determine analyte concentration. In this application note, we describe a method for identifying and quantifying unknowns in a single injection using a parallel Polyarc®/FID and mass spectrometer (MS).
ASTM D2163 and D5501 Analysis Comparison with Polyarc®/FID
Author(s): Major Petroleum Company, Contact Activated Research Company for References (contact@activatedresearch.com)
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ASTM D2163 (Standard test Method for Determination of Hydrocarbons in Liquefied Petroleum Gases and Propane/Propene Mixtures by Gas Chromatography) and ASTM D5501 (Standard Test Method for Determination of Ethanol and Methanol Content in Fuels Containing Greater than 20% Ethanol by Gas Chromatography) are routinely used in refinery laboratories. Both test methods require the use of response factors and were chosen to evaluate the effectiveness of the Polyarc system. As written test method ASTM D2163 gives users the option of using theoretical FID response factors or calculating response factors from the use of certified calibration standards. ASTM 5501 suggests typical mass response factors that are validated using multilevel calibration standards. Reported results for D2163 analysis are calculated using the theoretical response factors stated in the method relative to n-butane. Additionally, a demo “cryo sleeve” and updated “cryo block” were evaluated with the Polyarc reactor to allow the reactor to operate when cryogenic oven cooling is needed. The evaluation of ASTM D2163 was accomplished using a 150 meter column and cryogenic oven cooling. The GC conditions are listed below.
2016
Polyarc Microreactor: Quantification of Commercially Unavailable or Unknown Flavor Compounds.
Author(s): Jean-Paul Schirlé-Keller, Smaro Kokkinidou, and Devin Peterson, Flavor Research and Education Center at the University of Minnesota
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The Polyarc microreactor was used to quantify 2-acetyl-1-pyrroline (2AP) and 1-vinyl-2-pyrrolidone (1V2P) by gas chromatography (GC) analysis. Results were compared with internal standard quantification methods. The Polyarc microreactor reported comparable results when compared to traditional GC quantification techniques with the distinct advantage of not requiring a reference standard. Consequently, the Polyarc detector provided a more simple quantification instrumental setup that would also provide improved analysis of very complex extracts such as flavor solutions.
Hydrogen as a Carrier Gas in the Analysis of Polar/Non-Polar Compounds Using the Polyarc® System.
Author(s): Bob Moyer, Sr. Research Scientist, R&D, Sasol USA
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Utilizing the ARC Polyarc system and FID combination, hydrogen was evaluated as a carrier gas while investigating polar compounds known for potentially poor chromatographic peak shape and response factors. Compounds chosen were n-Decane, nOctanol, Aniline, m-Cresol, Triethyleneglycol (TEG), Catechol and n-Hexadecane. n-Decane and n-Hexadecane were included for comparison as more ideal compounds for chromatography and response factors. All compounds were treated as external standards between the levels of 0.2 – 5 weight % as carbon. Hydrogen (Air Liquide, Alphagaz1, 99.999% purity) was used as the column carrier gas to evaluate any potential effects on the reactor. All compounds showed good peak shape and the Polyarc/FID response factors between components narrowed significantly when compared to just FID response alone. In this study, no adverse effects where observed with hydrogen as the carrier gas. The small amount of hydrogen carrier flow kept the reactor conditioned while one could turn off the air/hydrogen to the reactor mass flow controller as well as the air to the FID during short standby periods.
Accurate Analysis of Fuel Ethers and Oxygenates in a Single Injection without Calibration Standards using GC-Polyarc®/FID.
Author(s): Andrew Jones, Activated Research Company
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The concentrations of oxygenates commonly used as fuel additives were determined with an average error of 1.7%, and within gravimetric uncertainties, using an ARC Polyarc reactor in series with a flame ionization detector (FID) on a gas chromatograph (GC). The analysis demonstrates a greater than 5-fold speed-up of analysis with less cost and less introduction of human error. This method is applicable to a wider range of volatile organic compounds (VOCs) that have importance in environmental and industrial testing.
GC/FID Analysis of Fatty Acid Methyl Esters without Correction Factors Using the Polyarc® Reactor.
Author(s): Andrew Jones, Activated Research Company
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An ARC Polyarc reactor was used in series with a flame ionization detector (FID) to analyze the composition of fatty acid methyl esters (FAMEs) in a mixture. By using this method, accurate quantification of 24 different FAMEs (C8 to C24) is demonstrated without the use of correction factors (response factors) and with a single internal standard (methyl tricosanoate) with an average error of 2.2%. The quantification error of C8 and C10 esters is significantly reduced compared with an analysis using FID and theoretical correction factors (from 9.7% to 5.6% and 3.1% to 0.3%, for C8 and C10, respectively). These results suggest that the accurate quantification of large mixtures of FAMEs is possible without calibration or theoretical correction factors because of the universal carbon response of the Polyarc/FID.
2015
Quantification of Pesticides in Food without Calibration using GC/FID with the Polyarc® Reactor.
Author(s): Charlie Spanjers and Paul Dauenhauer, University of Minnesota; Andrew Jones, Activated Research Company
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The quantification of pesticides in food using gas chromatography (GC) is traditionally a time-consuming process that involves the painstaking calibration of detector response for each analyte. The conversion of analytes to methane before their detection with a flame ionization detector (FID) results in a response that is proportional to the number of carbon atoms in the analytes and thereby eliminates the need for detector calibration. In this note, we use this approach and show the application of the Polyarc reactor to the quantification of dilute pesticides. The response factors of compounds in a commercial 22-component organochlorine pesticide mixture (200 µg/mL of each component) were 1.00 ± 0.09 with an average deviation from unity of 4%. This is compared to an FID-only analysis with response factors of 0.83 ± 0.10 with an average deviation from unity of 17%. Additional testing of the Polyarc reactor for six single-analyte pesticide solutions prepared from pure components provided response factors of 1.00 ± 0.04 with a mean deviation of 2%. Because all compounds have a response factor of one when using the Polyarc reactor, calibration to determine response factor is no longer required. We also show that direct-connect splitless liners prevent discrimination of analytes in the GC injector port.
Quantification of Liquid Hydrocarbons with Large Boiling Point Range using the Polyarc Reactor® Reactor.
Author(s): Charlie Spanjers and Paul Dauenhauer, University of Minnesota; Andrew Jones, Activated Research Company
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The conversion of analytes to methane before their detection with a flame ionization detector (FID) using gas chromatography (GC) gives more uniform analyte response. In this application note, we use the Polyarc® reactor to convert C5 to C18 n-alkanes to methane in order to quantify their concentrations. The Polyarc® reactor allows for accurate quantification (average error of 0.9%) of the hydrocarbons studied here. The Polyarc® reactor maintains high separation efficiency with only a 9% increase in peak width compared to an FID-only analysis. We demonstrate that low inlet pressures can lead to discrimination in the vaporization of hydrocarbons in the inlet, especially those with large differences in boiling points, and we describe methods for the optimization of inlet conditions to avoid these issues.
