• 한국축산식품학회지
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• 제34권6호
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• pp.749-756
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• 2014

A rapid and simple analytical method for L-carnitine was developed for infant and toddler formulas by liquid chromatography tandem mass spectrometry (LC-MS/MS). A 0.3 g of infant formula and toddler formula sample was mixed in a 50 mL conical tube with 9 mL water and 1 mL 0.1 M hydrochloric acid (HCl) to chemical extraction. Then, chloroform was used for removing a lipid fraction. After centrifuged, L-carnitine was separated and quantified using LC-MS/MS with electrospray ionization (ESI) mode. The precursor ion for L-carnitine was m/z 162, and product ions were m/z 103 (quantitative) and m/z 85 (qualitative), respectively. The results for spiked recovery test were in the range of 93.18-95.64% and the result for certified reference material (SRM 1849a) was within the range of the certificated values. This method could be implemented in many laboratories that require time and labor saving.

• Bulletin of the Korean Chemical Society
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• 제29권9호
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• pp.1755-1760
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• 2008

Energy minimization and conformational studies of molecular ions generated by ESI (electrospray ionization) tandem mass spectrometry (MS/MS) can be used for the discrimination of stereoisomeric permethylated and sodium cationized trisaccharides. Sets of fucose-containing trisaccharides having different internal and terminal linkages have been synthesized to analyze the reducing terminal linkage positions using BT and IT fusion approaches. A detailed investigation has been undertaken on the conformational behaviors of four trisaccharide fragments from human milk and blood group determinants of Type 1 and Type 2, namely Fuc($\alpha$1- 3)Gal($\beta$1-3)GalNAc and Fuc($\alpha$1-3)Gal($\beta$1-X)GlcNAc where X = 3, 4 and 6 using molecular modeling methods. Three dimensional rigid and adiabatic phi-psi-energy maps (Surfer program) describing the energy as a function of rotation around corresponding glycosidic linkages were calculated by SYBYL molecular modeling and MM4 force field programs conjunction with cleavage energies of ESI MS/MS for the side group orientations. This approach predicted conformational behaviors exhibited by isomer saccharides for future applications on biologically active glycoconjugates and to exploit a faster method of synthesizing a series of structural isomeric oligosaccharides.

• 대한화학회지
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• 제59권3호
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• pp.225-232
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• 2015

하천수 중에 7가지의 농약류(2,4-dichlorophenoxyacetic acid, 메소밀, 알디캅, MCPA, molinate, 카바릴, 카보퓨란)와 2가지의 합성원료(quinoline, 비스페놀-A)를 액체크로마토그래피 전자분무 이온화 질량분석법(liquid chromatography-electrospray ionization-tandem mass spectrometry, LC-ESI-MS/MS)을 사용하여 분석하였다. 분석물질들은 고체상 추출법(solid-phase extraction, SPE)을 사용하여 추출하였다. 용리액은 질소가스로 농축하였다. 잔여물에 30% 메탄올 수용액 100 μL를 재 용해시켜 0.2 μm PTFE 실린지 필터로 거른 후 그 일부를 LC-ESI-MS/MS에 직접 주입하여 분석하였다. 확립된 조건에서 검정곡선은 0.997 이상의 상관계수를 갖는 직선성을 보였다. 정량한계는 0.002~0.011 μg/L 이었고, 정밀도는 16.4% 이하였다. 또한 정확도는 84~107%의 범위를 보였고, 회수율은 56.2~98.6% 값을 나타내었다. 본 연구에서 개발한 분석법을 실제 하천수 분석에 적용하였다.

• Mass Spectrometry Letters
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• 제10권2호
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• pp.56-60
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• 2019

Coptidis Rhizoma (CR) has been used widely in traditional medicine to treat common diseases. This study aimed to develop a high-sensitivity liquid chromatography-tandem mass (LC-MS) spectrometry method for the evaluation of the pharmacokinetics of a new natural product that contain CR extract with the main bioactive compound, berberine, at trace concentrations. Human plasma samples were pretreated with methanol by a protein precipitation method. Berberine was analyzed on a Kinetex C18 column ($2.1mm{\times}50mm$, $100{\AA}$, $1.7{\mu}m$) using a mobile phase of 10 mM ammonium formate/0.1% formic acid in water (A) and acetonitrile (B) (50:50, v/v) with a flow rate of 0.25 mL/min. The analyte was detected by using electrospray ionization in positive mode with multiple reaction monitoring (MRM). The method was sensitive, with a lower limit of quantification of 1 pg/mL, which has not been previously obtained. The method was validated (over the range of 1-50 pg/mL) and applied successfully for the pharmacokinetic study of human plasma samples.

• Mass Spectrometry Letters
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• 제9권1호
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• pp.30-36
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• 2018

A quantitation method for free amino acids in human serum was developed using a stepwise-dilution method and a bimodal cation exchange (CEX)/hydrophilic interaction liquid chromatography (HILIC)-tandem mass spectrometry system equipped with an electrospray ionization source (ESI/MS/MS). This method, which was validated using quality control samples, was optimized for enhanced selectivity and sensitivity. Dithiothreitol (DTT) was used as a reducing agent to prevent the oxidation of a serum sample ($50{\mu}L$), which was then subjected to stepwise dilution using 3, 30, and 90 volumes of acetonitrile containing 0.1% formic acid. Chromatographic separation was performed on an Imtakt Intrada Amino Acid column ($50mm{\times}3mm$, $3{\mu}m$) in mixed mode packed with CEX and HILIC ligands embedded in the stationary phase. Underivatized free amino acids were eluted and separated within 10 min. As a result of the validation, the precision and accuracy for the inter- and intraday assays were determined as 2.11-11.51% and 92.82-109.40%, respectively. The lowest limit of quantification (LLOQ) was $0.5-4.0{\mu}g/mL$ and the matrix effect was 80.22-115.93%. The proposed method was successfully applied to the quantitative analysis of free amino acids in human serum.

• Bulletin of the Korean Chemical Society
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• 제33권11호
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• pp.3727-3734
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• 2012

An analytical method has been developed for the rapid determination of perfluorinated compounds (PFCs) in human serum samples. The extraction and purification of PFCs from human serum were performed by the modified method of previous report. Ten PFCs were rapidly separated within 3.3 min by C18-monolithic column liquid chromatography (LC) and detected by electrospray ionization (ESI) tandem mass spectrometry (MS/MS) in negative ion mode. The runtime of PFCs on monolithic column LC was up to 4-fold faster than that on conventional column LC. The effect of triethylamine (TEA) to the mobile phase has investigated on the overall MS detection sensitivity of PFCs in ESI ionization. Quantification was performed by LC-MS/MS in multiple-ion reaction monitoring (MRM) mode, using $^{13}C$-labeled internal standards. Method validation was performed to determine recovery, linearity, precision, and limits of quantification, followed by, the analysis of a standard reference material (SRM 1957 from NIST). The overall recoveries ranged between 81.5 and 106.3% with RSDs of 3.4 to 16.2% for the entire procedure. The calibration range extended from 0.33 to 50 $ng\;mL^{-1}$, with a correlation coefficient ($R^2$) greater than 0.995 and the limits of quantification with 0.08 to 0.46 $ng\;mL^{-1}$. This approach can be used for rapid and sensitive quantitative analysis of 10 PFCs in human serum with high performance and accuracy.

• Archives of Pharmacal Research
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• 제27권9호
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• pp.901-905
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• 2004

A rapid, sensitive and selective hydrophilic interaction liquid chromatography-tandem mass spectrometric(HILIC-MS/MS) method for the determination of tiapride in human plasma was developed. Tiapride and internal standard, metoclopramide were extracted from human plasma with dichloromethane at basic pH and analyzed on an Atlantis HILIC silica column with the mobile phase of acetonitrile-ammonium formate (190 mM, pH 3.0) (94：6, v/v). The ana-Iytes were detected using an electrospray ionization tandem mass spectrometry in the multi-ple-reaction-monitoring mode. The standard curve was linear (r＝0.999) over the concentration range of 1.00-200 ng/mL. The coefficient of variation and relative error for intra- and inter-assay at three QC levels were 6.4∼8.8％ and -2.0∼3.6％, respectively. The recoveries of tiapride ranged from 96.3 to 97.4％, with that of metoclopramide (internal standard) being 94.2％. The lower limit of quantification for tiapride was 1.00 ng/mL using 1 00 $\mu$L of plasma sample.

• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2425-2430
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• 2013

A simple, fast and robust analytical method was developed to determine imatinib in human plasma using liquid chromatography-tandem mass spectrometry with electrospray ionization in the positive ion mode. Imatinib and labeled internal standard were extracted from plasma with a simple protein precipitation. The chromatographic separation was performed using an isocratic elution of mobile phase involving 5.0 mM ammonium formate in water-5.0 mM ammonium formate in methanol (30:70, v/v) over 3.0 min on reversed-stationary phase. The detection was performed using a triple-quadrupole tandem mass spectrometer in multiple-reaction monitoring mode. The developed method was validated with lower limit of quantification of 10 ng/mL. The calibration curve was linear over 10-2000 ng/mL ($R^2$ > 0.99). The method validation parameters met the acceptance criteria. The spiked samples and standard solutions were stable under conditions for storage and handling. The reliable method was successfully applied to real sample analyses and thus a pharmacokinetic study in 27 healthy Korean male volunteers.

• Journal of Microbiology and Biotechnology
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• 제17권2호
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• pp.207-217
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• 2007

The Saccharomyces0 cerevisiae KNU5377 strain, which was isolated from spoilage in nature, has the ability to convert biomass to alcohol at high temperatures and it can resist against various stresses [18, 19]. In order to understand the defense mechanisms of the KNU5377 strain under menadione (MD) as oxidative stress, we used several techniques for study: peptide mass fingerprinting (PMF) by matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry (MS) followed by two-dimensional (2D) gel electrophoresis, liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS), and surface-enhanced laser desorption ionization-time of flight (SELDI-TOF) technology. Among the 35 proteins identified by MALDI-TOF MS, 19 proteins including Sod1p, Sod2p, Tsa1p, and Ahp1p were induced under stress condition, while 16 proteins were augmented under normal condition. In particular, five proteins, Sod1p, Sod2p, Ahp1p, Rib3p, Yaf9p, and Mnt1p, were induced in only stressed cells. By LC-ESI-MS/MS analysis, 37 proteins were identified in normal cells and 49 proteins were confirmed in the stressed cells. Among the identified proteins, 32 proteins were found in both cells. Five proteins including Yel047cp and Met6p were only upregulated in the normal cells, whereas 17 proteins including Abp1P and Sam1p were elevated in the stressed cells. It was interesting that highly hypothetical proteins such as Ynl281wp, Ygr279cp, Ypl273wp, Ykl133cp, and Ykr074wp were only expressed in the stressed cells. SELDI-TOF analysis using the SAX2 and WCX2 chips showed that highly multiple-specific protein patterns were reproducibly detected in ranges from 2.9 to 27.0 kDa both under normal and stress conditions. Therefore, induction of antioxidant proteins, hypothetical proteins, and low molecular weight proteins were revealed by different proteomic techniques. These results suggest that comparative analyses using proteomics might contribute to elucidate the defense mechanisms of KNU5377 under MD stress.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.821-827
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• 2014

An isotope dilution liquid chromatography tandem mass spectrometry (ID LC-MS/MS) method has been developed and applied to the determination of arsenobetaine (AsB, ${(CH_3)_3}^+AsCH_2COO^-$) from oyster candidate certified reference material (CRM). The exact matching isotope dilution approach was adopted for accurate determination of AsB using $^{13}C_2$-labeled AsB as an internal standard. Efficiencies of different AsB extraction methods were evaluated using a codfish reference material and a simple sonication method was selected as the method of choice for the certification of the oyster candidate CRM. The hydrophilic interaction liquid chromatography (HILIC) combined with electrospray ionization tandem mass spectrometry (ESI/MS/MS) in selected reaction monitoring (SRM) mode was optimized for adequate chromatographic retention and robust quantification of AsB from codfish and oyster samples. By analyzing 12 subsamples taken from each 12 bottles systematically selected from the whole oyster CRM batch, the certified value of AsB was determined as $6.60mg{\cdot}kg^{-1}{\pm}0.31mg{\cdot}kg^{-1}$ and it showed excellent between-bottle homogeneity of less than 0.42%, which is represented by relative standard deviation of 12 bottles from the CRM batch. The major source of uncertainty was the certified value of the AsB standard solution.