Boron forms unexpected glycopeptide derivatives during MALDI‐MS experiment

Nishikaze, Takashi; Kawabata, Shin-ichirou; Tanaka, Kōichi

doi:10.1002/jms.3246

Cited by 11 publications

(9 citation statements)

References 19 publications

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“…This facilitated specific detection and imaging of catecholamines in adrenal medulla (Figure 6). Further, the unique isotopic pattern of the boron atom ( 10 B and 11 B natural abundances of 19.9 and 80.1%, respectively) 55 While the specific properties of the derivatizing agent were tailored to LDI-MS experiments (stable charge and UV absorption), it was envisaged that there might also be benefits for ToF-SIMS analysis. The addition of a stable charge can aid detection and the shift in molecular mass may move the target analytes to a "cleaner" m/z range and reduce isobaric interferences.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

On-Tissue Chemical Derivatization of Catecholamines Using 4-(N-Methyl)pyridinium Boronic Acid for ToF-SIMS and LDI-ToF Mass Spectrometry Imaging

et al. 2018

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The analysis of small polar compounds with ToF-SIMS and MALDI-ToF-MS have been generally hindered by low detection sensitivity, poor ionization efficiency, ion suppression, analyte in-source fragmentation, and background spectral interferences from either a MALDI matrix and/or endogenous tissue components. Chemical derivatization has been a well-established strategy for improved mass spectrometric detection of many small molecular weight endogenous compounds in tissues. Here, we present a devised strategy to selectively derivatize and sensitively detect catecholamines with both secondary ion ejection and laser desorption ionization strategies, which are used in many imaging mass spectrometry (IMS) experiments. Chemical derivatization of catecholamines was performed by a reaction with a synthesized permanent pyridinium-cation-containing boronic acid molecule, 4-(N-methyl)pyridinium boronic acid, through boronate ester formation (boronic acid−diol reaction). The derivatization facilitates their sensitive detection with ToF-SIMS and LDI-ToF mass spectrometric techniques. 4-(N-Methyl)pyridinium boronic acid worked as a reactive matrix for catecholamines with LDI and improved the sensitivity of detection for both SIMS and LDI, while the isotopic abundances of the boron atom reflect a unique isotopic pattern for derivatized catecholamines in MS analysis. Finally, the devised strategy was applied, as a proof of concept, for on-tissue chemical derivatization and GCIB-ToF-SIMS (down to 3 μm per pixel spatial resolution) and LDI-ToF mass spectrometry imaging of dopamine, epinephrine, and norepinephrine in porcine adrenal gland tissue sections. MS/MS using collision-induced dissociation (CID)-ToF-ToF-SIMS was subsequently employed on the same tissue sections after SIMS and LDI mass spectrometry imaging experiments, which provided tandem MS information for the validation of the derivatized catecholamines in situ. This methodology can be a powerful approach for the selective and sensitive ionization/detection and spatial localization of diol-containing molecules such as aminols, vic-diols, saccharides, and glycans along with catecholamines in tissue sections with both SIMS and LDI/MALDI-MS techniques.

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Section: ■ Results and Discussionmentioning

confidence: 99%

On-Tissue Chemical Derivatization of Catecholamines Using 4-(N-Methyl)pyridinium Boronic Acid for ToF-SIMS and LDI-ToF Mass Spectrometry Imaging

et al. 2018

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“…Furthermore, it is di cult to remove excess reagents and, in many cases, residual reagents reduce the ionization e ciency in MS. It should be noted that contamination by boron compounds, which is a major component of reducing reagents, can cause the unintended formation of multiple boron adducts in glycans, decreasing analytical performance in MALDI-MS. 21) As a sensitive and MALDI-suited labeling method, Rohmer et al reported on the use of a solid matrix 3-aminoquinoline (3-AQ) as a labeling reagent. 22) is reaction takes place on a MALDI target, and 3-AQ plays the role not only of a labeling reagent but also of a MALDI matrix; hence, a puri cation step is no longer required.…”

Section: Labeling Of Glycansmentioning

confidence: 99%

Sensitive and Structure-Informative <i>N</i>-Glycosylation Analysis by MALDI-MS; Ionization, Fragmentation, and Derivatization

Nishikaze

2017

Mass Spectrometry

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Mass spectrometry (MS) has become an indispensable tool for analyzing post translational modi cations of proteins, including N-glycosylated molecules. Because most glycosylation sites carry a multitude of glycans, referred to as "glycoforms," the purpose of an N-glycosylation analysis is glycoform pro ling and glycosylation site mapping. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has unique characteristics that are suited for the sensitive analysis of N-glycosylated products. However, the analysis is o en hampered by the inherent physico-chemical properties of N-glycans. Glycans are highly hydrophilic in nature, and therefore tend to show low ion yields in both positive-and negative-ion modes.e labile nature and complicated branched structures involving various linkage isomers make structural characterization di cult. is review focuses on MALDI-MS-based approaches for enhancing analytical performance in N-glycosylation research. In particular, the following three topics are emphasized: (1) Labeling for enhancing the ion yields of glycans and glycopeptides, (2) Negative-ion fragmentation for less ambiguous elucidation of the branched structure of N-glycans, (3) Derivatization for the stabilization and linkage isomer discrimination of sialic acid residues.

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“…It is well known that liquids such as water, methanol, and tri fluoroacetic acid become contaminated with boron compounds when they are stored in borosilicate glass containers. [1][2][3][4][5] We recently reported that the boron compounds leach into methanol from borosilicate glass bottles, and interfere with the electrospray ionization mass spectral analysis of hydroxy acids such as malic acid, lactic acid, citric acid, tartaric acid, serine, threonine, and salicylic acid. 6 These compounds give borate anions consisting of two divalent anions and one boron atom for example, ion a in the case of tartaric acid.…”

Section: Introductionmentioning

confidence: 99%

Simple Mass Spectrometric Method for the Estimation of Boron and Aluminum in Water at the Parts per Billion Level

Krishnan

Pachaiappan

Vairamani

2015

Eur J Mass Spectrom (Chichester)

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The coordinating nature of the hydroxy carboxylic acids, such as tartaric and citric acids, has been utilized for the in-situ formation of anions representing the trivalent elements boron and aluminum and two dianions of the hydroxy acid selected under negative electrospray ionization mass spectral conditions. The abundance of these ions could be used for the quantification of boron and aluminum in water at concentrations ranging from 4.0 ppb to 535.0 ppb. For a period of six months, the validity of this method was tested with citric acid as the coordinating agent. Thus, the developed method offers a simple means for the quantification of boron and aluminum in water by negative electrospray ionization mass spectrometry with a single quadrupole mass spectrometer.

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Boron forms unexpected glycopeptide derivatives during MALDI‐MS experiment

Cited by 11 publications

References 19 publications

On-Tissue Chemical Derivatization of Catecholamines Using 4-(N-Methyl)pyridinium Boronic Acid for ToF-SIMS and LDI-ToF Mass Spectrometry Imaging

On-Tissue Chemical Derivatization of Catecholamines Using 4-(N-Methyl)pyridinium Boronic Acid for ToF-SIMS and LDI-ToF Mass Spectrometry Imaging

Sensitive and Structure-Informative <i>N</i>-Glycosylation Analysis by MALDI-MS; Ionization, Fragmentation, and Derivatization

Simple Mass Spectrometric Method for the Estimation of Boron and Aluminum in Water at the Parts per Billion Level

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