Abstract
The spatial distribution of neutral lipids and hydrocarbons has been imaged using MALDI-TOF mass spectrometry on intact plant and insect surfaces, namely wings and legs of the gray flesh fly (Neobellieria bullata), wings of common fruit fly (Drosophila melanogaster), leaves of thale cress (Arabidopsis thaliana), and leaves of date palm tree (Phoenix sp.). The distribution of wax esters (WEs) and saturated and unsaturated hydrocarbons (HCs) was visualized. The samples were attached on a target and multiply sprayed with lithium or sodium 2,5-dihydroxybenzoate. The deposits were homogenous, consisting of small islands (50–150 µm) of matrix crystals separated by small areas (10 µm) of uncovered cuticle. Samples of N. bullata wings were found to contain HCs and WEs distributed close to their basal parts. The distribution of sodium and potassium ions was visualized on samples prepared by sublimation of 2,5-dihydroxybenzoic acid. Pheromonal dienes were detected on D. melanogaster female wings. A homogenous distribution of saturated WEs was observed on A. thaliana and Phoenix sp. leaf samples. The optimum number of laser shots per pixel was found to be higher than for polar compounds imaging.
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Brucker, J. S. Cuticular Polar Lipids of Insects. In Insect Lipids: Chemistry, Biochemistry, and Biology, Stanley-Samuelson, D. W.; Nelson, D. R., Eds.; University of Nebraska Press: Lincoln, NE, 1993; pp 227–270.
Nelson, D. R.; Blomquist, G. J. Insect Waxes. In Waxes: Chemistry, Molecular Biology, and Functions, Hamilton, R. J., Ed.; The Oily Press: Dundee, Scotland, 1995; pp 1–90.
Blomquist, G. J.; Howard, R. W. Pheromone biosynthesis in social insects. In Insect Pheromone Biochemistry and Molecular Biology: The Biosynthesis and Detection of Pheromones and Plant Volatiles, Blomquist, G. J.; Vogt, R. g., Eds.; Academic Press: London, UK, 2003; p. 332.
Howard, R. W.; Blomquist, G. J. Ecological, Behavioral, and Biochemical Aspects of Insect Hydrocarbons. Annu. Rev. Entomol. 2005, 50, 371–393.
Howard, R. W. Cuticular Hydrocarbons and Chemical Communication. In Insect Lipids: Chemistry, Biochemistry and Biology, Stanley-Samuelson, D. W.; Nelson, D. R., Eds.; University of Nebraska Press: Lincoln, NE, 1993; pp 179–226.
Espelie, K. E.; Bernays, E. A.; Brown, J. J. Plant and Insect Cuticular Lipids Serve as Behavioral Cues for Insects. Arch. Insect. Biochem. Physiol. 1991, 17, 223–233.
Juniper, B. E. Waxes on Plant Surfaces and Their Interactions with Insects. In Waxes: Chemistry, Molecular Biology, and Functions, Hamilton, R. J., Eds.; The Oily Press: Dundee, Scotland, 1995; pp 157–174.
Haverty, M. I.; Nelson, L. J. Cuticular Hydrocarbons of Reticulitermes (Isoptera rhinotermitidae) from Northern California Indicate Undescribed Species. Comp. Biochem. Physiol. B Biochem. Mol. Biol. 1997, 118, 869–880.
Ferveur, J. F. The Pheromonal Role of Cuticular Hydrocarbons in Drosophila melanogaster. Bioessays 1997, 19, 353–358.
Bianchi, G. Plant Waxes. In Waxes: Chemistry, Molecular Biology, and Functions, Hamilton, R. J., Ed.; The Oily Press: Dundee, Scotland, 1995; pp 175–222.
Kunst, L.; Samuels, A. L. Biosynthesis and Secretion of Plant Cuticular Wax. Prog. Lipid Res. 2003, 42, 51–80.
Samuels, L.; Kunst, L.; Jetter, R. Sealing Plant Surfaces: Cuticular Wax Formation by Epidermal Cells. Annu. Rev. Plant. Biol. 2008, 59, 683–707.
Post-Beittenmiller, D. Biochemistry and Molecular Biology of Wax Production in Plants. Annu. Rev. Plant Physiol. Plant. Mol. Biol. 1996, 47, 405–430.
Neinhuis, C.; Koch, K.; Barthlott, W. Movement and Regeneration of Epicuticular Waxes Through Plant Cuticles. Planta 2001, 213, 427–434.
Bargel, H.; Koch, K.; Cerman, Z.; Neinhuis, C. Structure-Function Relationships of the Plant Cuticle and Cuticular Waxes—a Smart Material? Funct. Plant. Biol. 2006, 33, 893–910.
Christie, W. W. Lipid Analysis; The Oily Press: Bridgewater, England, 2003; pp 105–372.
Christie, W. W. Gas Chromatography and Lipids: A Practical Guide; The Oily Press: Ayr, Scotland, 1989; pp 64–80.
Byrdwell, W. C. Atmospheric Pressure Ionization Techniques in Modern Lipid Analysis. In Modern Methods for Lipid Analysis by Liquid Chromatography/Mass Spectrometry and Related Techniques, Byrdwell, W. C., Ed.; AOCS Press: Champaign, IL, 2005; p. 1–18.
Schiller, J.; Suss, R.; Arnhold, J.; Fuchs, B.; Lessig, J.; Muller, M.; Petkovic, M.; Spalteholz, H.; Zschornig, O.; Arnold, K. Matrix-Assisted Laser Desorption and Ionization Time-of-Flight (MALDI-TOF) Mass Spectrometry in Lipid and Phospholipid Research. Prog. Lipid Res. 2004, 43, 449–488.
Asbury, G. R.; Al-Saad, K.; Siems, W. F.; Hannan, R. M.; Hill, H. H. Analysis of Triacylglycerols and Whole Oils by Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry. J. Am. Soc. Mass Spectrom. 1999, 10, 983–991.
Cvačka, J.; Svatoš, A. Matrix-Assisted Laser Desorption/Ionization Analysis of Lipids and High Molecular Weight Hydrocarbons with Lithium 2,5-Dihydroxybenzoate Matrix. Rapid Commun. Mass Spectrom. 2003, 17, 2203–2207.
Cvačka, J.; Jiroš, P.; Šobotník, J.; Hanus, R.; Svatoš, A. Analysis of Insect Cuticular Hydrocarbons Using Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry. J. Chem. Ecol. 2006, 32, 409–434.
Vrkoslav, V.; Míková, R.; Cvačka, J. Characterization of Natural Wax Esters by MALDI-TOF Mass Spectrometry. J. Mass Spectrom. 2009, 44, 101–110.
Jetter, R.; Schaffer, S.; Riederer, M. Leaf Cuticular Waxes are Arranged in Chemically and Mechanically Distinct Layers: Evidence from Prunus laurocerasus L. Plant Cell Environ 2000, 23, 619–628.
Waku, Y.; Manable, Y. Fine Structure of the Wax Gland in a Scale Insect, Eriococcus lagerstraemiae Kuwana (Homoptera: Eriococcidae). Appl. Entomol. Zoolog. 1981, 16, 94–102.
Foldi, I.; Pesrce, M. J. Fine Structure of Wax Glands, Wax Morphology, and Function in the Female Scale Insect, Pulvinaria regalis Canard. (Hemiptera: Coccidae). Int. J. Insect Morphol. Embryol. 1985, 14, 259–271.
McDonnell, L. A.; Heeren, R. M. A. Imaging mass spectrometry. Mass Spectrom. Rev. 2007, 26, 606–643.
Monroe, E. B.; Jurchen, J. C.; Lee, J.; Rubakhin, S. S.; Sweedler, J. V. Vitamin E Imaging and Localization in the Neuronal Membrane. J. Am. Chem. Soc. 2005, 127, 12152–12153.
Touboul, D.; Roy, S.; Germain, D. P.; Chaminade, P.; Brunelle, A.; Laprevote, O. MALDI-TOF and Cluster-TOF-SIMS Imaging of Fabry Disease Biomarkers. Int. J. Mass Spectrom. 2007, 260, 158–165.
Tahallah, N.; Brunelle, A.; Porte, S.; Laprevote, O. Lipid Mapping in Human Dystrophic Muscle by Cluster-Time-of-Flight Secondary Ion Mass Spectrometry Imaging. J. Lipid Res. 2008, 49, 438–454.
Schwartz, S. A.; Reyzer, M. L.; Caprioli, R. M. Direct Tissue Analysis Using Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry: Practical Aspects of Sample Preparation. J. Mass Spectrom. 2003, 38, 699–708.
Hankin, J. A.; Barkley, R. M.; Murphy, R. C. Sublimation as a Method of Matrix Application for Mass Spectrometric Imaging. J. Am. Soc. Mass Spectrom. 2007, 18, 1646–1652.
Puolitaival, S. M.; Burnum, K. E.; Cornett, D. S.; Caprioli, R. M. Solvent-Free Matrix Dry-Coating for MALDI Imaging of Phospholipids. J. Am. Soc. Mass Spectrom. 2008, 19, 882–886.
Chen, Y.; Allegood, J.; Liu, Y.; Wang, E.; Cachon-Gonzalez, B.; Cox, T. M.; Merrill, A. H.; Sullards, M. C. Imaging MALDI Mass Spectrometry Using an Oscillating Capillary Nebulizer Matrix Coating System and Its Application to Analysis of Lipids in Brain from a Mouse Model of Tay-Sachs/Sandhoff Disease. Anal. Chem. 2008, 80, 2780–2788.
Caprioli, R. M.; Farmer, T. B.; Gile, J. Molecular Imaging of Biological Samples: Localization of Peptides and Proteins using MALDI-TOF MS. Anal. Chem. 1997, 69, 4751–4760.
Chaurand, P.; Caprioli, R. M. Direct Profiling and Imaging of Peptides and Proteins from Mammalian Cells and Tissue Sections by Mass Spectrometry. Electrophoresis 2002, 18, 3125–3135.
Wang, H.-Y. J.; Jackson, S. N.; McEuen, J.; Woods, A. S. Localization and Analyses of Small Drug Molecules in Rat Brain Tissue Sections. Anal. Chem. 2005, 77, 6682–6686.
Khatib-Shahidi, S.; Andersson, M.; Herman, J. L.; Gillespie, T. A.; Caprioli, R. M. Direct Molecular Analysis of Whole-Body Animal Tissue Sections by Imaging MALDI Mass Spectrometry. Anal. Chem. 2006, 78, 6448–6456.
Hsieh, Y.; Casale, R.; Fukuda, E.; Chen, J.; Knemeyer, I.; Wingate, J.; Morrison, R.; Korfmacher, W. Matrix-Assisted Laser Desorption/Ionization Imaging Mass Spectrometry for Direct Measurement of Clozapine in Rat Brain Tissue. Rapid Commun. Mass Spectrom. 2006, 20, 965–972.
Shroff, R.; Vergara, F.; Muck, A.; Svatos, A.; Gershenzon, J. Nonuniform Distribution of Glucosinolates in Arabidopsis thaliana Leaves Has Important Consequences for Plant Defense. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 6196–6201.
Rujoi, M.; Estrada, R.; Yappert, M. C. In situ MALDI-TOF MS Regional Analysis of Neutral Phospholipids in Lens Tissue. Anal. Chem. 2004, 76, 1657–1663.
Woods, A. S.; Jackson, S. N. Brain Tissue Lipidomics: Direct Probing Using Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry. AAPS J. 2006, 8, E391-E395.
Jones, J. J.; Borgmann, S.; Wilkins, C. L.; O’Brien, R. M. Characterizing the Phospholipid Profiles in Mammalian Tissues by MALDI FTMS. Anal. Chem. 2006, 78, 3062–3071.
Trim, P. J.; Atkinson, S. J.; Princivalle, A. P.; Marshall, P. S.; West, A.; Clench, M. R. Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging of Lipids in Rat Brain Tissue with Integrated Unsupervised and Supervised Multivariant Statistical Analysis. Rapid Commun. Mass Spectrom. 2008, 22, 1503–1509.
Stransky, K.; Jursik, T. Simple Quantitative Transesterification of Lipids. 1: Introduction. Fett/Lipid 1996, 98, 65–71.
Aasen, A. J.; Hofstetter, H. H.; Iyengar, B. T. R.; Holman, R. T. Identification and Analysis of Wax Esters by Mass Spectrometry. Lipids 1971, 6, 502–507.
Jackson, L. L.; Armold, M. T.; Regnier, F. E. Cuticular Lipids of Adult Fleshflies. Sarcophaga bullata. Insect Biochem. 1974, 4, 369–379.
Armold, M. T.; Regnier, F. E. A Developmental Study of the Cuticular Hydrocarbons of Sarcophaga bullata. J. Insect. Physiol. 1975, 21, 1827–1833.
Jallon, J. M.; David, J. R. Variations in Cuticular Hydrocarbons Along the Eight Species of the Drosophila melanogaster subgroup. Evolution 1987, 41, 294–302.
Yew, J. Y.; Cody, R. B.; Kravitz, E. A Cuticular Hydrocarbon Analysis of an Awake Behaving Fly Using Direct Analysis in Real-Time Time-of-Flight Mass Spectrometry. Proc. Natl. Acad. Sci. U.S.A. 2008, 20, 7135–7140.
Garcia, B.; Marco, J. A.; Seoane, E.; Tortajada, A. Triterpenes, Waxes, and Tricin in Phoenix canariensis. J. Nat. Prod. 1981, 44, 111–113.
Lai, C.; Kunst, L.; Jetter, R. Composition of Alkyl esters in the Cuticular Wax on Inflorescence Stems of Arabidopsis thaliana cer mutants. Plant J. 2007, 50, 189–196.
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Published online October 12, 2009
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Vrkoslav, V., Muck, A., Cvačka, J. et al. MALDI imaging of neutral cuticular lipids in insects and plants. J Am Soc Mass Spectrom 21, 220–231 (2010). https://doi.org/10.1016/j.jasms.2009.10.003
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DOI: https://doi.org/10.1016/j.jasms.2009.10.003