• Mass Spectrometry Letters
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• 제12권2호
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• pp.41-46
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• 2021

Collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) are the widely used fragmentation technique in mass spectrometry-based proteomics studies. Understanding the fragmentation pattern from the tandem mass spectra using statistical methods helps to implement efficient spectrum analysis algorithms. The study characterizes the frequency of occurrence of multi-charged fragment ions and their neutral loss events of doubly and triply charged peptides in the CID and HCD spectrum. The dependency of the length of the fragment ion on the occurrence of multi-charged fragment ion is characterized here. Study shows that the singly charged fragment ions are generally dominated in the doubly charged peptide spectrum. However, as the length of the product ion increases, the frequency of occurrence of charge 2 fragment ions increases. The y- ions have more tendencies to generate charge 2 fragment ions than b- ions, both in CID and HCD spectrum. The frequency of occurrence of charge 2 fragment ion peaks is prominent upon the dissociation of the triply charged peptides. For triply charged peptides, product ion of higher length occurred in multiple charge states in CID spectrum. The neutral loss peaks mostly exist in charge 2 states in the triply charged peptide spectrum. The b-ions peaks are observed in much less frequency than y-ions in HCD spectrum as the length of the fragment increases. Isotopic peaks are occurred in charge 2 state both in doubly and triply charged peptide's HCD spectrum.

• 생약학회지
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• 제10권2호
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• pp.55-59
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• 1979

Mass spectra of the dammarane triterpenes having open side chain and $C_{20}-C_{25}-epoxy$ side chain were measured. Principal fragment ions were assigned and plausible mechanisms for the formation of the fragment ions were proposed. In general, the triter-penoids of $C_{20}-C_{25}-epoxy$ side chain. produce $h_{1}-species$ fragment ions by the deletion of side chain at $C_{20}-C_{22}$ bond and open side chain triterpenoids produce $h_{2}$ species fragmentions whose mass numbers are higher by two mass unit than those of $h_{1}$ species. The mass number of h species fragment ions will serve as the diagnostic tool for the elucidation of side chain structure of tetracyclic triterpenoids.

• Bulletin of the Korean Chemical Society
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• 제21권8호
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• pp.785-792
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• 2000

Mass spectral fragmentations of six chlorinated organophosphorus pesticides were investigated using electron impact mass spectrometry. Understanding the fragmentation pathways, based on the fragment ions of mass spectra, should be useful in the structural elucidation and chemical identification of these compounds. The pro-posed fragmentation pathways were verified by collision-induced dissociation B/E-linked scan spectra. ln most cases,the structures of characteristic fragment ions could be expected by the observation of the peak clusters due to 35Cl and 37Cl isotopes. According to substituted groups on phosphorus atom, phosphate and phospho-rothioate exhibited significantIy differentfragmentation patterns. Especially, phosphate and phosphorothioate with diethyl ester produced more diverse fragment ions than that with dimethyl ester.

• 분석과학
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• 제30권6호
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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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• 제25권10호
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• pp.1538-1544
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• 2004

Fragmentations and proton transfer reactions of mono-, di-, and triethanolamines were studied using FTMS. It was found that the most abundant fragment ion was $[M-CH_2OH]^+$. The $[M-CH_2OH-H_2O]^+$ was observed in the mass spectra of diethanolamine and triethanolamine. By increasing the ion trapping time in the ICR cell, the $[M+H]^+$ and $[M+H-H_2O]^+$ ions were notably increased for all the samples while the $[M+H-2H_2O]^+$ was observed in the mass spectra of diethanolamine and triethanolamine. The proton transfer reactions between the fragment ions and neutral molecules occurred predominantly by increasing the ion trapping time. The rate constants for the proton transfer reactions were calculated from experimental results. The proton transfer reaction of $CHO^+$ was the fastest one, which is consistent with the heats of reaction. The rate constants for proton transfer reactions of triethanolamine were much slower than those of ethanolamine and diethanolamine because of the steric hindered structure of triethanolamine. The plausible structures of observed ions and heats of reaction for proton transfer were calculated with AM1 semiempirical method.

• Mass Spectrometry Letters
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• 제10권2호
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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.

• 분석과학
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• 제9권1호
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• pp.1-12
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• 1996

열에 불안정하면서 -OH기를 함유하는 미지의 화합물은 LC/TSP/MS에서 [${MNH_4}^+$] 이온, [$MH^+$] 이온, 그리고 [$MH^+-OH$] 이온의 생성이 가능하며, 이들 이온의 m/z값의 차이가 17로서 같기 때문에 이들의 생성 정도에 따라 분자량 추정에 혼란이 일어날 수가 있었다. 따라서 다른 보완 가능한 실험결과가 요구되며 $CF_3COOD+NH_4OH$ 이온화 용액을 사용하여 그 유용성을 검토하였다. 또한 LC/TSP/MS에서 생성되는 토막이온들이 필라멘트의 전자살에 의해 생성되는 것인지 아니면 다른 어떤 생성기전이 존재하는지를 검토하였다.

• Bioinformatics and Biosystems
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• 제1권2호
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• pp.109-114
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• 2006

프로테오믹스에서 얻는 탄뎀 질량 스펙트럼은 효소로 가수분해된 펩타이드의 전구이온(precursor ion) 분자량과 펩타이드에 에너지를 가하여 생성된 이온조각(fragment ion)들의 분자량값들로 구성된다. 탄뎀 질량스펙트럼의 전구이온 분자량은 단백질 서열 데이터베이스에서의 검객 과정에서 가장 먼저 고려하는 값이다. 단백질 검색 프로그램은 단백질 서열 중에 스펙트럼의 전구이온으로부터 계산된 분자량과 일치하는 펩타이드 서열들을 찾아내고, 이들 중의 하나를 이온조각들의 분자량 정보를 이용해서 선택한다. 이 때에 전구이온의 분자량은 사용자가 지정한 오차범위 내에서 일치하는 감을 검색하는데, 이때의 오차범위는 질량분석기의 정확도에 따라 결정된다. 본 논문에서는 인간 혈액의 혈장시료로부터 FT LTQ 질량분석기를 통해 얻어진 탄뎀 질량 스펙트럼에서 전구이온 분자량의 분포를 역순서열을 이용하여 분석하였다. 전구이온 분자량의 분포를 재해석하여 실험값의 정확도를 보정하고 단백질 동정의 성능을 향상시키는 방법을 모색하였다.

• Bulletin of the Korean Chemical Society
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• 제18권8호
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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.

• 보존과학회지
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• 제34권2호
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• pp.129-135
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• 2018

Scientific investigation of cultural heritage can provide important information to understand the context of the object. To know the characteristics of the material is also an essential part of objects management and conservation. However, the identification and characterization of organic dyes used in archaeological and historical textiles are often limited by the restrictions in sampling. To cope with the difficulties, applications of high-performance techniques of surface analysis, such as Time of Flight-Secondary Ion Mass Spectra (TOF-SIMS) could be considered as a non or micro-destructive option. This study aims to examine the applicability of TOF-SIMS analysis to the detection of organic dyes from historical textiles. A group of silk fabrics dyed with vegetable dyes were artificially photo-aged to different degrees and analyzed with TOF-SIMS. Molecular and fragment ions from indigo were successfully detected from the aged samples; however, only some fragment ions were observed from gardenia and safflower dyed fabrics. Further studies with actual historical samples with extended examination scope would be necessary to assess the validity of this technique.