title: Development of "Laser Ablation Direct Analysis in Real Time Imaging" Mass Spectrometry: Application to Spatial Distribution Mapping of Metabolites Along the Biosynthetic Cascade Leading to Synthesis of Atropine and Scopolamine in Plant Tissue.
abstract: Methods for the accomplishment of small-molecule imaging by mass spectrometry are challenged by the need for sample pretreatment steps, such as cryo-sectioning, dehydration, chemical fixation, or application of a matrix or solvent, that must be performed to obtain interpretable spatial distribution data. Furthermore, these steps along with requirements of the mass analyzer such as high vacuum, can severely limit the range of sample types that can be analyzed by this powerful method. Here, we report the development of a laser ablation-direct analysis in real time imaging mass spectrometry approach which couples a 213 nm Nd:YAG solid state UV laser to a direct analysis in a real time ion source and high-resolution time-of-flight mass spectrometer. This platform enables facile determination of the spatial distribution of small-molecules spanning a range of polarities in a diversity of sample types and requires no matrix, vacuum, solvent, or complicated sample pretreatment steps. It furnishes high-resolution data, can be performed under ambient conditions on samples in their native form, and results in little to no fragmentation of analytes. We demonstrate its application through determination of the spatial distribution of molecules involved in the biosynthetic cascade leading to formation of the clinically relevant alkaloids atropine and scopolamine in Datura leichhardtii seed tissue.
authors.affiliation: State University of New York at Albany , Department of Chemistry, 1400 Washington Avenue, Albany, New York 12222, United States.
authors.forename: Kristen L
authors.initials: KL
authors.lastname: Fowble
authors.affiliation: JEOL Ltd. , 3-1-2 Musashino, Akishima, Tokyo, Japan 196-8558.
authors.forename: Kanae
authors.initials: K
authors.lastname: Teramoto
authors.affiliation: JEOL USA Inc. , 11 Dearborn Road, Peabody, Massachusetts 01960, United States.
authors.forename: Robert B
authors.initials: RB
authors.lastname: Cody
authors.affiliation: JEOL USA Inc. , 11 Dearborn Road, Peabody, Massachusetts 01960, United States.
authors.forename: David
authors.initials: D
authors.lastname: Edwards
authors.affiliation: JEOL USA Inc. , 11 Dearborn Road, Peabody, Massachusetts 01960, United States.
authors.forename: Donna
authors.initials: D
authors.lastname: Guarrera
authors.affiliation: State University of New York at Albany , Department of Chemistry, 1400 Washington Avenue, Albany, New York 12222, United States.
authors.forename: Rabi A
authors.identifier: 0000-0002-3135-4130
authors.initials: RA
authors.lastname: Musah
mesh_terms: D001285:Atropine / Q000096:biosynthesis* / Q000737:chemistry / Q000378:metabolism; D032302:Datura / Q000737:chemistry* / Q000378:metabolism; D007834:Lasers; D013058:Mass Spectrometry; D015394:Molecular Structure; D012601:Scopolamine / Q000737:chemistry / Q000378:metabolism*; D012639:Seeds / Q000737:chemistry / Q000378:metabolism; D013997:Time Factors; D014466:Ultraviolet Rays
chemical_list: D001285:Atropine; D012601:Scopolamine