• Bulletin of the Korean Chemical Society
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• v.26 no.9
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• pp.1347-1353
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• 2005

Sets of sialic acid-containing trisaccharides having different internal and terminal linkages have been synthesized to develop a sensitive method for analysis of the reducing terminal linkage positions. The trisaccharides, sialyl($\alpha$ 2-3)Gal($\beta$ 1-3)GalNAc and sialyl($\alpha$ 2-3)Gal($\beta$ 1-X)GlcNAc where X=3, 4 and 6, were synthesized and examined using electrospray ionization (ESI)-collision induced dissociation (CID) tandem mass spectrometry (MS/MS). The compounds chosen for this study are related to terminal groups likely to be found on polylactosamine-like glycoproteins and glycolipids which occur on the surface of mammalian cells. The purpose of this study is to develop tandem mass spectrometral methods to determine detailed carbohydrate structures on permethylated or partially methylated oligosaccharides for future applications on biologically active glycoconjugates and to exploit a faster method of synthesizing a series of structural isomeric oligosaccharides to be used for further mass spectrometry and instrumental analysis.

• Mass Spectrometry Letters
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• v.8 no.4
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• pp.90-97
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• 2017

Androgenic anabolic steroids (AASs) are synthetic derivatives of testosterone with a common structure containing cyclopentanoperhydrophenanthrene nucleus. Their use enhances the muscle building capacity and is beneficial during performance. The AASs are one of the most abused group of substances in horse doping. Liquid chromatography tandem mass spectrometry ($LC/MS^n$) has been successfully applied to the detection of anabolic steroids in biological samples. However, the saturated hydroxysteroids viz: nandrolone, $5{\alpha}-estrane-3{\beta}$, $17{\alpha}-diol$ exhibit lower detection responses in electrospray ionisation (ESI) because of their poor ionisation efficiency. To overcome this limitation pre-column chemical derivatization has been introduced to enhance their detection responses in $LC-ESI-MS^n$ analysis. The aim of present study was to develop a sensitive method for identification and confirmation of nandrolone and its metabolite in horse urine incorporating pre-column derivatization using picolinic acid. The method consists of extraction of targeted steroid conjugates by solid phase extraction (SPE). The eluted steroid conjugates were hydrolysed by methanolysis and free steroids were recovered with liquid-liquid extraction. The resulting steroids were derivatized to form picolinoyl esters and identification was done using LC-ESI-MS/MS in positive ionization mode. The picolinated steroid adduct enhanced the detection levels in comparison to underivatized steroids.

• Mass Spectrometry Letters
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• v.5 no.1
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• pp.1-11
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• 2014

Lipids play important roles in biological systems; they store energy, play a structural role in the cell membrane, and are involved in cell growth, signal transduction, and apoptosis. Phospholipids (PLs) in particular have received attention in the medical and lipidomics research fields because of their involvement in human diseases such as diabetes, obesity, atherosclerosis, and many cancers associated with lipid metabolic disorders. Here I review experimental strategies for PL analysis based on nanoflow liquid chromatography-electrospray ionization-tandem mass spectrometry (nLC-ESI-MSn). In particular, discussed are lipid extraction methods, nanoflow LC separation of PLs, effect of ionization modifiers on the ESI of PLs, influence of chain lengths and unsaturation degree of acyl chains of PLs on MS intensity, structural determination of the molecular structure of PLs and their oxidized products, and quantitative profiling of PLs from biological samples such as tissue, urine, and plasma in relation to cancer and coronary artery disease.

• Mass Spectrometry Letters
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• v.2 no.1
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• pp.16-19
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• 2011

Oxidation products of ceftiofur were formed in hydrogen peroxide solution. The structures of the ceftiofur oxidation products were characterized by high-performance liquid chromatography/electrospray ionization/tandem mass spectrometry (HPLC/ESI/MS/MS). The products were identified as compounds oxidized at the sulfur of a cephem ring. For further analysis, experiments were performed using $O^{18}$-labeled hydrogen peroxide. In addition, density-functional calculations were carried out for six possible oxidation products to support the experimental results.

• Mass Spectrometry Letters
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• v.9 no.1
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• pp.17-23
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• 2018

Studies on the interactions of amyloidogenic proteins with trace metals, such as copper, have indicated that the metal ions perform a critical function in the early oligomerization process. Herein, we investigate the effects of Cu(II) ions on the active sequence regions of amyloidogenic proteins using electrospray ionization mass spectrometry (ESI-MS) and collision induced dissociation tandem MS (CID-MS/MS). We chose three amyloidogenic peptides NNQQNY, LYQLEN, and VQIVYK from yeast prion like protein Sup35, insulin chain A, and tau protein, respectively. [Cu-peptide] complexes for all three peptides were observed in the mass spectra. The mass spectra also show that increasing Cu(II) concentrations decrease the population of existing peptide oligomers. The tandem mass spectrum of NNQQNY shows preferential binding for the N-terminal region. All three peptides are likely to appear to be in a Cu-monomer-monomer (Cu-M-M) structure instead of a monomer-Cu-monomer (M-Cu-M) structure.

• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.575-578
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• 2005

Electrospray ionization mass spectrometry (ESI MS) was used, along with gas chromatography-mass spectrometry (GC-MS), to monitor Paal-Knorr synthesis of 2,5-dimethyl-1-phenylpyrrole by condensation of aniline with 2,5-hexanedione. In addition to 2,5-dimethyl-1-phenylpyrrole observed as a single spot by TLC, unexpected dimer size compounds were observed by GC-MS. Dimers and trimers were observed by ESI MS. ESI tandem mass spectrometry was used to select plausible structures for the dimer. ESI MS with or without liquid chromatographic separation is useful for observing oligomeric byproducts with low volatility produced in organic reactions.

• BMB Reports
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• v.43 no.11
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• pp.761-765
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• 2010

Salivary testosterone levels in Korean adults were quantitatively measured for the first time by liquid chromatography-electrospray-tandem mass spectrometry (LC ESI MS/MS). Salivary testosterone was separated on a multiple reaction monitoring (MRM) chromatogram within 7 min. The LC ESI MS/MS assay was validated over the linearity range of 0.01-2.00 ng/ml (r=0.99987) using testosterone-$d_3$ as an internal standard. The lower limit of quantification (LOQ) was 0.01 ng/ml. The intra- and inter-assay precisions were 1.54% to 4.09% and 0.96% to 4.29%, respectively. The mean recovery was 93.32% (range 88.43-98.05%). The validated assay was then applied to measure the salivary testosterone levels of Korean adults. In men, the salivary testosterone level collected between 9：00-11：00 am was approximately 2.8 times higher than that in women (P < 0.0001). Salivary testosterone levels in both sexes negatively correlated with age. The present assay would also be useful in measuring salivary testosterone levels in clinical laboratories.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.397-401
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• 2009

The complexes of $C_2-\;and\;C_6$-dihydroceramides with transition metal ions have been investigated by using Electrospray ionization-tandem mass spectrometry (ESI-MS/MS). The formation and fragmentation pathways of several doubly charged cluster ions as well as singly charged cluster ions of $C_2-\;and\;C_6$-dihydroceramides with transition metal ions have studied by ESI-MS/MS in the positive mode. Under ESI conditions, dihydroceramides form singly and doubly charged complexes with transition metal ions $(Mn^{2+},\;Fe^{2+},\;Co^{2+},\;Ni^{2+},\;and\;Zn^{2+}\;except\;Cu^{2+})$ with the compositions of $[DHCer+M+2H^2O-H]^+,\;[2DHCer+M+2H2O-H]^+,\;[3DHCer+M+2H2O-H]^+,\;[2DHCer+M]^{2+},\;[3DHCer+M]^{2+},\;[4DHCer+M]^{2+},\;[5DHCer+M]^{2+},\;and\;[6DHCer+M]^{2+}\;(DHCer\;=\;C_2-\;or\;C_6$-dihydroceramide, M = transition metal ion). The different complexation behavior of copper is responsible for relatively lower affinity of dihydroceramides to copper compared to those of other transition metals. It is also found that in the mass spectrum of the dihydroceramide complexes with copper(II), [2DHCer+Cu-H]$^+$ was observed with considerable intensity as well as [2DHCer+Cu+2$H_2O-H]^+$ due to its different geometry from those of other metals.

• 대한임상약리학회:학술대회논문집
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• 2007.11a
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• pp.92-93
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• 2007

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• Analytical Science and Technology
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• v.14 no.5
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• pp.384-391
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• 2001

In this study, a new quantitative analytical method has been developed for the rapid determination of acylcarnitines and amino acids in human blood using electrospray ionization / tandem mass spectrometry (ESI-MS/MS). Acylarmitines and amino acids were analyzed by tandem mass spectrometry after conversion to their butylesters through treatment with 3N butanolic hydrogen chloride. Acylcrnitines were analyzed using precursor 85 ion scan and alanine, valine, leucine/isoleucine, methionine, phenylalanine, tyrosine, aspartic acid and glutamic acid were analyzed using neutral loss 102 scan, ornitine and citrulline were analyzed neutral loss 119 scan, glycine was analyzed using neutral loss 56 scan, arginine was analyzed using neutral loss 161 scan and argininosuccinic acid was analyzed product ion 459 scan. This method reduced sample preparation time compared to that with conventional amino acid analyzer and liquid chromatography, with high sensitivity and good reproducibility.