Gas-phase basicity of several common MALDI matrices measured by a simple experimental approach

Barylyuk, Konstantin; Fritsche, Lukas; Balabin, Roman M.; Nieckarz, Robert J.; Zenobi, Renato

doi:10.1039/c1ra01117k

Cited by 5 publications

(3 citation statements)

References 81 publications

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“…The calculated GBs for SA matrix may also be compared to a small number of values previously reported in the literature. In general, the GB values determined from these studies are somewhat higher than the earlier calculated literature values of 845.1 kJ/mol, 866.6 kJ/mol, 867.4 kJ/mol and the earlier experimental GBs of 869.0 kJ/mol and 860.5 kJ/mol . It should be noted that these earlier determinations did not account for the influence of a higher effective temperature and were generally determined for room temperature SA.…”

Section: Resultscontrasting

confidence: 74%

Investigations of the Equilibrium Conditions in Plumes of Laser Desorbed Sinapic Acid with Amino Acid Analytes: Influence of Sample Preparation and Matrix to Analyte Ratio

Elliott

Kinsel

2020

J. Am. Soc. Mass Spectrom.

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The equilibrium nature of a plume of laser desorbed material is examined through the application of a previously developed thermodynamic model to the ion signals observed in 337 nm MALDI mass spectra of mixtures of the matrix sinapic acid with the amino acids alanine, valine, isoleucine, and phenylalanine. Samples are prepared using both conventional dried-droplet and solvent-free methods for comparison. The relative yield of protonated amino acid is shown to increase as the amino acid gas-phase basicity increases for both sample preparation methods. Matrix gas phase basicity values extracted from the equilibrium plots are shown to be in good agreement ([M − H + ] • 876 kJ/mol and [M] 879 kJ/mol) with published experimental values supporting a mechanism wherein the protonated sinapic acid and/or the matrix radical cation act as the proton donor species. These experiments further reveal that there is a large difference in the extracted plume effective temperatures with the solvent-free method yielding lower effective temperatures as compared to the dried-droplet sample preparation, e.g., 552 K versus 1296 K, respectively, at M/A 1:1 (mole/mole). In addition, these experiments suggest that plume effective temperatures decrease as the relative amount of matrix deposited with the analyte increases, regardless of the sample preparation method. Cumulatively, these observations suggest that the crystalline solid allows more efficient transfer of the photoexcitation energy during the sample desorption step, as compared to the solvent-free sample, and/or collisional cooling is more effective for the plume of material desorbed from the solvent-free sample as compared to the conventional dried-droplet sample.

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Section: Resultscontrasting

confidence: 74%

Investigations of the Equilibrium Conditions in Plumes of Laser Desorbed Sinapic Acid with Amino Acid Analytes: Influence of Sample Preparation and Matrix to Analyte Ratio

Elliott

Kinsel

2020

J. Am. Soc. Mass Spectrom.

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“…Gas-phase (or intrinsic) basicity (GB) of a basic molecule is its important property, largely determining its basicity also in solution and being directly important, for example, in various types of laser desorption mass spectrometry methods, − and in electrospray ionization (ESI) liquid chromatography (LC) mass spectrometry (MS) methods. − …”

Section: Introductionmentioning

confidence: 99%

Experimental Basicities of Phosphazene, Guanidinophosphazene, and Proton Sponge Superbases in the Gas Phase and Solution

et al. 2016

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Experimental gas-phase superbasicity scale spanning 20 orders of magnitude and ranging from bicyclic guanidine 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene to triguanidinophosphazenes and P3 phosphazenes is presented together with solution basicity data in acetonitrile and tetrahydrofuran. The most basic compound in the scale-triguanidinophosphazene Et-N═P[N═C(NMe2)2]3-has the highest experimental gas-phase basicity of an organic base ever reported: 273.9 kcal mol(-1). The scale includes besides the higher homologues of classical superbasic phosphazenes and several guanidino-substituted phosphazenes also a number of recently introduced bisphosphazene and bis-guanidino proton sponges. This advancement was made possible by a newly designed Fourier transform ion cyclotron resonance (ICR) mass spectrometry setup with the unique ability to generate and control in the ICR cell sufficient vapor pressures of two delicate compounds having low volatility, which enables determining their basicity difference. The obtained experimental gas-phase and solution basicity data are analyzed in terms of structural and solvent effects and compared with data from theoretical calculations.

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“…Good agreement was found between the experimentally measured and computationally predicted basicities except for CHCA for which the calculations resulted in a value of approximately 80 kJ/mol low. This discrepancy was attributed to a gas‐phase rearrangement of CHCA into the more stable heterocyclic aromatic isomer, 7‐hydroxyquinoline‐3‐carboxylic acid ( 2 ) (Barylyuk et al, ). Sodium cation affinities of the commonly used MALDI matrices, nicotinic acid ( 1/20 ), quinoline ( 7/10 ), 3‐aminoquinoline (3‐AQ, 1/24 ), 4‐nitroaniline ( 3/3 ), picolinic acid ( 3/2 ), and 3‐hydroxypicolinic acid have been determined by guided ion beam tandem mass spectrometry, again with good agreement with calculated values (Chinthaka & Rodgers, 2012).…”

Section: Theorymentioning

confidence: 99%

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2011–2012

Harvey

2015

Mass Spectrometry Reviews

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This review is the seventh update of the original article published in 1999 on the application of MALDI mass spectrometry to the analysis of carbohydrates and glycoconjugates and brings coverage of the literature to the end of 2012. General aspects such as theory of the MALDI process, matrices, derivatization, MALDI imaging, and fragmentation are covered in the first part of the review and applications to various structural types constitute the remainder. The main groups of compound are oligo- and poly-saccharides, glycoproteins, glycolipids, glycosides, and biopharmaceuticals. Much of this material is presented in tabular form. Also discussed are medical and industrial applications of the technique, studies of enzyme reactions, and applications to chemical synthesis. © 2015 Wiley Periodicals, Inc. Mass Spec Rev 36:255-422, 2017.

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Gas-phase basicity of several common MALDI matrices measured by a simple experimental approach

Cited by 5 publications

References 81 publications

Investigations of the Equilibrium Conditions in Plumes of Laser Desorbed Sinapic Acid with Amino Acid Analytes: Influence of Sample Preparation and Matrix to Analyte Ratio

Investigations of the Equilibrium Conditions in Plumes of Laser Desorbed Sinapic Acid with Amino Acid Analytes: Influence of Sample Preparation and Matrix to Analyte Ratio

Experimental Basicities of Phosphazene, Guanidinophosphazene, and Proton Sponge Superbases in the Gas Phase and Solution

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2011–2012

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