--A "Little" Mass Spectrometry and Sailing--

New 5/22/05! Matrix Effects in LCMS:  Matrix effects in LCMS can affect sensitivity, precision and accuracy.  We have developed a simple way to monitor phospholipids and lysophospholipids which yield matrix effects.  This approach is easily used in developing MRM LC-MS-MS analyses.

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Updated 8/10/03! New NIST Search Program (Version 2): Our Standard Corporate Method for Searching MS Databases:  New NIST search program with a Windows’ Standard interface and many new capabilities (e.g. Structure Searching!) is available.  We are successfully using this approach to search, share, and maintain our proprietary EI, commercial EI, MS/MS, TSCA, and Plant Material databases.  It can easily interface to any PC-mass spec data processing application.

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Identification of Components in Polycarbonate and Polyester Monomers and Polymers by GC-MS:  We employ three different GC-MS methods for this work:  ammonia (protonated and deuterated) chemical ionization, deuterated ammonia EI, derivatization (protonated and deuterated trimethylsilylation) GC-MS.  In addition, a general method for the hydrolysis and GC-MS analysis of polycarbonate and polyester polymers is described.
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Identification of Unknowns in Competitive Products Using LC/MS Data and TSCA Inventory:  Unknowns in competitive samples are identified with either LC/MS/MS data or LC/MS “in-source” fragmentation data.  The molecular weight information and fragmentation data are used with the TSCA list to identify the unknown.

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This section includes information on the choice of amines as chemical ionization reagent gases.  Ammonia is normally adequate for most applications.  However, gas mixtures of other alkylamines with methane can yield less fragmentation data and resolve ambiguous ammonia CI data.  Deuterated amononia and alkyl amines can distinguish isomeric compounds in some cases.

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We use a wide variety of chemical ionization gases in our laboratory for the molecular weight determination of unknowns. In the link below, a versatile chemical ionization manifold is described that can be retrofitted to any commercial mass spectrometer. The paper includes plans for building it, operating it, and maintaining it.

 

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Updated 8/10/03! Normally silylation reactions give the desired derivative in high yields. However, sometimes artifacts (by-products) are formed. The paper linked below lists all the types of artifacts noted in our laboratory in the last 20 years and ones we have found in the literature. It is a modified (not refereed) copy of a paper [J.L. Little, J. Chromatogr. A, 844 (1999) 1-22] containing additional examples found since the paper was published. Reprints also available by U.S. Mail upon E-mail request.

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Diazomethane and Trimethylsilyl-diazomethane reactions are often employed to increase the volatility and stability of organic acids for gas chromatography mass spectrometry. Normally the reactions give the desired methyl ester derivatives. However, sometimes artifacts (by-products are noted. The paper linked below lists all the types of artifacts noted in our laboratory in the last 15 years and ones we have found in the literature. Also, convenient methods for producing small amounts of diazomethane and for utilizing both reagents are described.

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Updated 8/10/03! Eastman Chemical Company employs both Magnetic and Time-of-flight (TOF) instruments for accurate mass measurements.  Our results on magnetic instruments are compared (181 points) to values obtained from The Journal of Organic Chemistry (197 laboratories, 1280 points).  Also limitations of time-to-digital TOF technology is discussed and a modeling “program” shared. 

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Normally doubly charged ions are relatively small in electron impact mass spectra. However, we noted one that was almost the base peak in a phosphate! If you have seen any this large before or have a suggested mechanism, e-mail me. I would also be interested in seeing other examples.

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“Sailing Away on TVA" might seem like a somewhat ridiculous statement and Upper East Tennessee might seem like a strange place to learn how to sail. However, there are a lot of opportunities if you just look around. There is an Eastman Chemical Company Sailing Club, a Watauga Lake Sailing Club, and a variety of classes offered by local groups.

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Surfactant Identification by LCMS-We have been been very successful in the identification of surfactants by electrospray LCMS using Residual Molecular Weight, Molecular Weight, and NIST library searches of in-source CID spectra.  5-Function data files are obtained in positive (low and high cone), negative (low and high cone), and diode array UV-VIS.  The low cone gives MW information, the high fragmentation information, i.e. substructural information.

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Questions or Comments?

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Eastman Chemical Company