• 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.

• 한국전기전자재료학회논문지
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• 제15권7호
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• pp.576-582
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• 2002

Nonvolatile semiconductor memory devices with reoxidized nitrided oxide(RONO) gate dielectrics were fabricated, and nitrogen distribution and bonding species which contribute to memory characteristics were analyzed. Also, memory characteristics of devices depending on the anneal temperatures were investigated. The devices were fabricated by retrograde twin well CMOS processes with $0.35\mu m$ design rule. The processes could be simple by in-situ process in growing dielectric. The nitrogen distribution and bonding states of gate dielectrics were investigated by Dynamic Secondary Ion Mass Spectrometry(D-SIMS), Time-of-Flight Secondary Ion Mass Spectrometry(ToF-SIMS), and X-ray Photoelectron Spectroscopy(XPS). As the nitridation temperature increased, nitrogen concentration increased linearly, and more time was required to form the same reoxidized layer thickness. ToF-SIMS results showed that SiON species were detected at the initial oxide interface which had formed after NO annealing and $Si_2NO$ species within the reoxidized layer formed after reoxidation. As the anneal temperatures increased, the device showed worse retention and degradation properties. It could be said that nitrogen concentration near initial interface is limited to a certain quantity, so the excess nitrogen is redistributed within reoxidized layer and contribute to electron trap generation.

• 한국환경과학회지
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• 제11권4호
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• pp.367-373
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• 2002

The polycyclic aromatic hydrocarbons(PAHs) content in sewage sludge was determined by gas chromatography linked to ion trap mass spectrometry(GC/ITMS) with five deuterated PAHs as internal standards. The minimum detection limit was from 1.66 to 7.14 pg for individual PAH by GC/ITMS. For determining total PAHs(∑PAH) in sewage sludge 84 samples from 74 waste water treatment plants in whole country were analyzed. The average content of ∑PAH far whole samples was 3,289$\pm$3,098 $\mu\textrm{g}$/kg, and ranged from 142 to maximum 20,102 $\mu\textrm{g}$/kg. According to the number of population of the city, the areas were classified as five regions, ie. big, large, middle, small, and rural area in which the waste water treated plants were grown. The contents of PAHs were 4,689$\pm$5,503, 5,839$\pm$6,401, 3,725$\pm$2,053, 2,237$\pm$2,069, and 2,475$\pm$1,489 $\mu\textrm{g}$/kg, in big, large, middle, small, and rural area, respectively.

• Mass Spectrometry Letters
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• 제2권3호
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• pp.69-72
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• 2011

Defective synthesis of the steroid hormones by the adrenal cortex has profound effects on human development and homeostasis. Due to the time-consuming chromatography procedure combined with mass spectrometry, the matrix-assisted laser desorption ionization method coupled to the linear ion-trap tandem mass spectrometry (MALDI-LTQ-MS/MS) was developed for quantitative analysis of 10 adrenal steroids in human serum. Although MALDI-MS can be introduced for its applicability as a high-throughput screening method, it has a limitation on reproducibility within and between samples, which renders poor reproducibility for quantification. For quantitative MALDI-MS/MS analysis, the stable-isotope labeled internal standards were used and the conditions of crystallization were tested. The precision and accuracy were 3.1~35.5% and 83.8~138.5%, respectively, when a mixture of 10 mg/mL ${\alpha}$-cyano-4-hydroxycinnamic acid in 0.2% TFA of 70% acetonitrile was used as the MALDI matrix. The limit of quantification ranged from 5 to 340 ng/mL, and the linearity as a correlation coefficient was higher than 0.988 for all analytes in the calibration range. Clinical applications include quantitative analyses of patients with congenital adrenal hyperplasia. The devised MALDI-MS/MS technique could be successfully applied to diagnosis of clinical samples.

• Archives of Pharmacal Research
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• 제28권10호
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• pp.1190-1195
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• 2005

The objective of this study was to develop an assay for mequitazine (MQZ) for the study of the bioavailability of the drug in human subjects. Using one mL of human plasma, the pH of the sample was adjusted and MQZ in the aqueous phase extracted with hexane; the organic layer was then evaporated to dryness, reconstituted and an aliquot introduced to a gas chromatograph/mass spectrometer (GC/MS) system with ion-trap detector. Inter- and intra-day precision of the assay were less than 15.1 and $17.7{\%}$, respectively; Inter- and intra-day accuracy were less than 8.91 and $18.6{\%}$, respectively. The limit of quantification for the current assay was set at 1 ng/mL. To determine whether the current assay is applicable in a pharmacokinetic study for MQZ in human, oral formulation containing 10 mg MQZ was administered to healthy male subjects and blood samples collected. The current assay was able to quantify MQZ levels in most of the samples. The maximum concentration ($C_{max}$ was 8.5 ng/mL, which was obtained at 10.1 h, with mean half-life of approximately 45.5 h. Under the current sampling protocol, the ratio of $AUC_{t{\rightarrow}last}$ to $AUC_{t{\rightarrow}{\infty}}$ was $934{\%}$, indicating that the blood collection time of 216 h is reasonable for MQZ. Therefore, these observations indicate that an assay for MQZ in human plasma is developed by using GC/MS with ion-trap detector and validated for the study of pharmacokinetics of single oral dose of 10 mg MQZ, and that the current study design for the bioavailability study is adequate for the drug.

• 한국군사과학기술학회지
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• 제7권3호
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• pp.110-121
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• 2004

Pyrolysis-mass spectrometry, incorporating an in situ thermal hydrolysis and methylation(THM) step, has been used to study biological materials for bacteria, toxin and virus. Newly developed pyrolyzer was used to decompose biological materials, and tetramethylammonium hydroxide(TMAH) was used as a methylation reagent. Chemical ionization(CI) using ethanol and ion trap mass spectrometer(ITMS) were used to ionize and analyze of pyrolysis components, respectively. Analytical characteristics of bacteria (including spore), virus and toxin were analyzed. Also acquisition and interpretation of mass spectra as biomarkers for classification/identification of biological material s were explained.

• Bulletin of the Korean Chemical Society
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• 제26권8호
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 추계학술대회 논문집
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• pp.17-20
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• 2001

Nonvolatile semiconductor memory devices with reoxidized nitrided oxide(RONO) gate dielectric were fabricated, and nitrogen distribution and bonding species which contributing memory characteristics were analyzed. Also, memory characteristics of devices according to anneal temperatures were investigated. The devices were fabricated by 0.35$\mu\textrm{m}$ retrograde twin well CMOS processes. The processes could be simple by in-situ process of nitridation anneal and reoxidation. The nitrogen distribution and bonding state of gate dielectric were investigated by Dynamic Secondary Ion Mass Spectrometry(D-SIMS), Time-of-Flight Secondary ton Mass Spectrometry(ToF-SIMS), and X-ray Photoelectron Spectroscopy(XPS). Nitrogen concentrations are proportional to nitridation anneal temperatures and the more time was required to form the same reoxidized layer thickness. ToF-SIMS results show that SiON species are detected at the initial oxide interface and Si$_2$NO species near the new Si-SiO$_2$ interface that formed after reoxidation. As the anneal temperatures increased, the device showed worse retention and degradation properties. These could be said that nitrogen concentration near initial interface is limited to a certain quantity, so excess nitrogen are redistributed near the Si-SiO$_2$ interface and contributed to electron trap generation.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.709-714
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• 2014

Protein tyrosine nitration is considered as an important indicator of nitrosative stresses and as one of the main factors for pathogenesis of inflammation and neuronal degeneration. In this study, we investigated various nitrosative modifications of bovine carbonic anhydrase II (CAII) through qualitative and semi-quantitative analysis using the combined strategy of Fourier transformation ion cyclotron resonance mass spectrometry (FT-ICR MS) and ion-trap tandem mass spectrometry (IT-MS/MS). FT-ICR MS and its spectra were used for the search of the pattern of nitrosative modifications. Identification of nitrosatively modified tyrosine sites were executed through IT-MS/MS. In addition, we also tried to infer the reason for the site-specific nitrosative modifications in CAII. In view of the above purpose, we have explored- i) the side chain accessibility, ii) the electrostatic environment originated from the acidic/basic amino acid residues neighboring to the nitrosatively modified site and iii) the existence of competing amino acid residues for nitration.

• Mass Spectrometry Letters
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• 제4권2호
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• pp.30-33
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• 2013

Chalcones are naturally occurring, biologically active molecules generating interest from a wide range of research applications including synthetic methodology development, biological activity investigation and studying fragmentation patterns. In this article, a series of chalcones has been synthesized and their fragmentation behavior was studied using modern ambient ionization technique Direct Analysis in Real Time (DART). DART ion source connected with an ion trap mass spectrometer was used for the fragmentation of various substituted chalcones. The chalcones were introduced to the DART source using a glass capillary without sample preparation step. All the chalcones showed prominent molecular ion peaks $[M]^{{\cdot}+}$ corresponding to the structures. Multistage mass spectral data $MS^n$ ($MS^2$ and $MS^3$) were collected for all the chalcones studied. The chalcones with substitutions at 3, 4 or 5 positions gave product ion peaks with the loss of a phenyl radical ($Ph^{\cdot}$) by radical initiated ${\alpha}$-cleavage, while substitution at 2 position of chalcone in the A-ring gave a product ion peak with the loss of substituted styryl radical (PhCH = $CH^{\cdot}$). In case of the chalcones with the substituent at 4 positions in A and B rings gave both types of fragmentation patterns. In conclusion, chalcones can be easily characterized using modern DART interface in very short time and efficiently without any cumbersome sample pretreatment.