title: Z-sinapinic acid: the change of the stereochemistry of cinnamic acids as rational synthesis of a new matrix for carbohydrate MALDI-MS analysis.
abstract: Successful application of matrix-assisted laser desorption/ionization (MALDI) MS started with the introduction of efficient matrices such as cinnamic acid derivatives (i.e. 3,5-dimethoxy-4-hydroxycinnamic acid, SA; α-cyano-4-hydroxycinnamic acid). Since the empirical founding of these matrices, other commercial available cinnamic acids with different nature and location of substituents at benzene ring were attempted. Rational design and synthesis of new cinnamic acids have been recently described too. Because the presence of a rigid double bond in its molecule structure, cinnamic acids can exist as two different geometric isomers, the E-form and Z-form. Commercial available cinnamic acids currently used as matrices are the geometric isomers trans or E (E-cinnamic and trans-cinnamic acids). As a new rational design of MALDI matrices, Z-cinnamic acids were synthesized, and their properties as matrices were studied. Their performance was compared with that of the corresponding E-isomer and classical crystalline matrices (3,5-dihydroxybenzoic acid; norharmane) in the analysis of neutral/sulfated carbohydrates. Herein, we demonstrate the outstanding performance for Z-SA. Sulfated oligosaccharides were detected in negative ion mode, and the dissociation of sulfate groups was almost suppressed. Additionally, to better understand the quite different performance of each geometric isomer as matrix, the physical and morphological properties as well as the photochemical stability in solid state were studied. The influence of the E/Z photoisomerization of the matrix during MALDI was evaluated. Finally, molecular modeling (density functional theory study) of the optimized geometry and stereochemistry of E-cinnamic and Z-cinnamic acids revealed some factors governing the analyte-matrix interaction.
authors.affiliation: CIHIDECAR-Departamento de Química Orgánica, FCEN, Universidad de Buenos Aires, Pabellón II, 3er P, Ciudad Universitaria, 1428, Buenos Aires, Argentina.
authors.forename: María L
authors.initials: ML
authors.lastname: Salum
authors.forename: Lucia M
authors.initials: LM
authors.lastname: Itovich
authors.forename: Rosa
authors.initials: R
authors.lastname: Erra-Balsells
mesh_terms: D002241:Carbohydrates / Q000737:chemistry; D002934:Cinnamates / Q000737:chemistry*; D003373:Coumaric Acids / Q000737:chemistry*; D008958:Models, Molecular; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods*; D013237:Stereoisomerism
chemical_list: D002241:Carbohydrates; D002934:Cinnamates; D003373:Coumaric Acids; C029010:cinnamic acid; C073734:sinapinic acid
keywords: E-coumaric acid; E-ferulic acid; E-sinapinic acid; Z-coumaric acid; Z-ferulic acid; Z-sinapinic acid; neutral carbohydrates; sulfated carbohydrates