• Bulletin of the Korean Chemical Society
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• v.26 no.8
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• pp.1235-1240
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• 2005

A combination of electrospray ionization and tandem mass spectrometry was used to characterize the scavenging reactions of acrylamide (AA) in the presence of glutathione (GSH) in vitro. In the presence of GSH, AA was deactivated effectively and scavenged by reactions consuming small amount of GSH. Reaction products and structural information were identified using collision-induced dissociation (CID) in an ion trap mass spectrometer. In the mixture of GSH and AA, significant increase in abundance of fragment ion peak was observed at m/z 233, which was identified as $[Cys-Glu]^+$, formed by the elimination of glycine moiety of GSH. GSH also contributes to the AA scavenging reaction by conjugating with AA through the sulfhydryl group in cysteine moiety. The probable scavenging reaction pathway of AA in the presence of GSH has been proposed based on the CID experimental data.

• Analytical Science and Technology
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• v.10 no.1
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• pp.9-17
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• 1997

Nitrophenols are a group of important priority pollutants classified by the US Environmental Protection Agency. Reverse-phase liquid chromatographic method combined with mass spectromethy employing atmospheric pressure chemical ionization(APCI) interface is utilized to determine a mixture of nitrophenols in water matrix without any pretreatment. The sensitivity and selectivity for the identification of different kind of nitrophenols is enhanced by the use of selected ion monitoring and cone voltage fragmentation. The fragmentation patterns of nitrophenols are compared with those obtained from the collision induced dissociation(CID) MS/MS technique.

• Bulletin of the Korean Chemical Society
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• v.18 no.8
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• pp.874-880
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• 1997

Various classes of phospholipids were investigated for the structural determination of fatty acyl groups by fast atom bombardment tandem mass spectrometry (FAB-MS/MS). Phospholipids were desorbed by FAB as molecules chelated with sodium ion (or ions). Collision-induced dissociation (CID) of intact sodium adduct molecular ions ([M+Na]+, [M-H+2Na]+ or [M+Na-2H]-) produced a series of homologous fragment ions via the charge-remote fragmentation along the fatty acid chains. These ions were found useful to locate the double bond positions even for the polyunsaturated fatty acid chains. The regiospecificity of the acyl chain linkages in phosphatidylcholine (PC) could also be determined based on the ratio of relative abundance of the product ions (i.e., [M+Na-85-R2COOH]+ vs [M+Na-85-R1COOH]+) in CID-MS/MS of [M+Na]+. These are generated by the loss of fatty acyl groups at sn-1 and sn-2, respectively, together with the choline group. In all the phospholipid compounds investigated, loss of the fatty acid at the sn-2 position was dominant. The present method was applied to the structural determination of molecular species of phosphatidylglycerols (PG) isolated from cyanobacterium Synechocystis sp. PCC 6803.

• Mass Spectrometry Letters
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• v.10 no.2
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• pp.50-55
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• 2019

The fragmentation statistics of ion trap CID (Collision-Induced Dissociation) spectra using 87,661 tandem mass spectra of doubly charged tryptic peptides are analyzed here. In contrast to the usual method of using intensity information, the frequency of occurrence of fragment ions, with respect to the position of the cleavage site and the residues at these sites is studied in this paper. The analysis shows that the frequency of occurrence of fragment ion peaks is more towards the middle of the peptide than its ends. It was noted that amino acid with an aromatic and basic side chain at N- & C- terminal end of the peptide stimulates more peaks at the lower end of the spectrum. The residue pair effect was shown when the amide bond occurs between acidic and basic residues. The fragmentation at these sites (D/E-H/R/K) stimulates the generation of the y-ion peak. Also, the cleavage site H-H/R/K stimulates the generation of b-ions. K-P environment in the peptide sequence has more tendency to generate y-ions than b-ions. Statistical analysis helps in the visualization of the CID fragmentation pattern. Cleavage pattern along the length of the peptide and the residue pair effects, enhance the knowledge of fragmentation behavior, which is useful for the better interpretation of tandem mass spectra.

• Analytical Science and Technology
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• v.30 no.6
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• pp.379-389
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• 2017

In this study, we set up an analytical method that can be used for rapid and accurate determination of representative isoquinoline alkaloids in medicinal plants using UPLC-ESI-Q-TOF MS (ultra pressure liquid chromatography-electrospray ionization-quadrupole-time-of-flight mass spectrometry). The compounds were eluted on a C18 column with 0.1 % formic acid and acetonitrile, and separated with good resolution within 13 min. Each of the separated components was characterized by precursor ions (generated by ESI-Q-TOF) and fragment ions (produced by collision-induced dissociation, CID), which were used as a reliable database. We also performed method validation: analytes showed excellent linearity ($R^2$, 0.9971-0.9996), LOD (5-25 ng/mL), LOQ (17-82 ng/mL), accuracy (91.6-97.4 %) as well as intra- and inter-day precisions (RSD, 1.8-3.2 %). In the analysis of Chelidonium majus L., magnoflorine, coptisine, sanguinarine, berberine and palmatine were detected by matching retention times and characteristic fragment ion patterns of reference standards. We also confirmed that, among the quantified components, coptisine was present in the highest quantity. Furthermore, alkaloid profiling was carried out by analyzing the fragment ion patterns corresponding to peaks of unknown components. In this manner, protopine, chelidonine, stylopine, dihydroberberine, canadine, and nitidine were tentatively identified. We also proposed the molecular structure of the fragment ions that appear in the mass spectrum. Therefore, we concluded that our suggested method for the determination of major isoquinoline alkaloids by UPLC-Q-TOF can be useful not only for quality control, but also for rapid and accurate investigation of phytochemical constituents of medicinal plants.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1684-1688
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• 2013

A rapid and sensitive method for determining usnic acid of Lethariella cladonioides in rat was established using high performance liquid chromatography (HPLC) quadrupole time-of-flight (QTOF) tandem mass (MS/MS). Rat plasma was pretreated by mixture of acetonitrile and chloroform to precipitate plasma proteins. Chromatographic separation was achieved on a column ($50{\times}2.1$ mm, $5{\mu}m$) with a mobile phase consisting of water (containing $5{\times}10^{-3}$ M ammonium formate, pH was adjusted to 3.0 with formic acid) and acetonitrile (20:80, v/v) at a flow rate of 0.3 mL/min. A tandem mass spectrometric detection with an electrospray ionization (ESI) interface was conducted via collision induced dissociation (CID) under negative ionization mode. The MS/MS transitions monitored were m/z 343.0448 ${\rightarrow}$ m/z 313.2017 for usnic acid and m/z 153.1024 ${\rightarrow}$ m/z 136.2136 for protocatechuic acid (internal standard). The linear range was calculated to be 2.0-160.0 ng/mL with a detection limit of 3.0 pg/mL. The inter- and intra-day accuracy and precision were within ${\pm}7.0%$. Pharmacokinetic study showed that the apartment of usnic acid in vivo confirmed to be a two compartment open model. The method was fully valid and will probably be an alternative for pharmacokinetic study of usnic acid.

• Analytical Science and Technology
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• v.24 no.2
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• pp.78-84
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• 2011

The fragmentation patterns of a serine protease inhibitor, camostat, and its degradation product, 4-(4-guanidinobenzoyloxy)phenylacetic acid (GBPA), were for the first time investigated by a triple quadrupole tandem mass spectrometry equipped with an electrospray source (ESI-MS/MS) in positive and/or negative ion mode under collision-induced dissociation (CID). The positive CID spectrum of camostat showed distinctly that the single bond (C-O) cleavage between carbonyl group and oxygen atom of the ester bonds of the compound favorably occurred and then the loss of N,N-dimethylcarbamoylmethyl group was more susceptible than that of guanidine moiety. In the positive ion CID spectrum of GBPA, the initial cleavage between the carbonyl group and oxygen atom of 4-guanidinobenzoyloxy group also occurred, yielding the most abundant fragment ion at m/z 145. On the other hand, the negative CID spectrum of GBPA characteristically showed the occurrence of the most abundant peak at m/z 226 resulting from the sequential neutral losses of $CO_2$ and HN=C=NH from the parent ion at m/z 312.