• Bulletin of the Korean Chemical Society
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• 제28권7호
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• pp.1187-1194
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• 2007

The three major active isoflavonoids (calycosin-7-O-β -glucoside, isomucronulatol 7-O-β-glucoside, formononetin) and two main saponins (astragaloside I, astragaloside IV) in an extract of Radix Astragali were determined using rapid, sensitive, reliable HPLC/UV and LC-ESI-MS/MS methods. The separation conditions employed for HPLC/UV were optimized using a phenyl-hexyl column (4.6 × 150 mm, 5 μm) with the gradient elution of acetonitrile and water as the mobile phase at a flow rate of 1.0 mL/min and a detection wavelength of 230 nm. The specificity of the peaks was determined using a triple quadrupole tandem mass spectrometer equipped with an electrospray ionization (ESI) source that was operated in multiple reaction monitoring (MRM) in the positive mode. These methods were fully validated with respect to the linearity, accuracy, precision, recovery and robustness. The HPLC/UV method was applied successfully to the quantification of three major isoflavonoids in the extract of Radix Astragali. The results indicate that the established HPLC/UV and LC-ESI-MS/MS methods are suitable for the quantitative analysis and quality control of multi-components in Radix Astragali.

• 대한한방부인과학회지
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• 제26권4호
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• pp.48-65
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• 2013

Objectives: We took breast milk samples and analyzed them using HPLC and LC/MS/MS, to evaluate the effects of taking Saenghwa-tang during breastfeeding on breast milk. Methods: The study participants were 20 lactating women who admitted in Korean medical postpartum care center. Breast milks were collected from paticipants who have been administrated Saenghwa-tang for more than 3 days. We used HPLC and LC/MS/MS for the determinations of amygdalin, liquiritins, 6-gingerol, decursin and decursinol angelate in Saenghwa-tang. Results: 1. Participants' $Mean{\pm}S.D$ (standard deviation) of age is $31.05{\pm}1.96$, and 15 participants had normal delivery and 5 participants had cesarean delivery. 12 participants were primipara and 8 participants were multipara. $Mean{\pm}S.D$ of lactating date is $9.4{\pm}0.94$. 2. Using HPLC, we learned LOQ level peak that matches the peak retention time of standard components of Saenghwa-tang was not detected from 20 breast milk samples. 3. Using LC/MS/MS, decursin of Angelicae Gigantis Radix was detected from HMSP 02, HMSP 04, HMSP 06, HMSP 11, and the each concentrations are 16, 2, 64, 11 ppb. Liquiritin of Glycyrrhizae Radix was not detected from HMSP 13~HMSP 18. Conclusions: Data obtained by this approach shows that this method is reliable and suitable for determining the safety of taking Saenghwa-tang during breastfeeding.

• 분석과학
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• 제22권1호
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• pp.65-74
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• 2009

옻나무는 아시아지역 전역에 주로 분포하며 예로부터 도료 및 약용 식물로 많이 사용되어져 왔었다. 특히 우리나라에서 재배되는 옻나무가 그 기능이 더욱 우수하다고 알려져 있는데 그 원인은 명확히 밝혀진 바가 없다. 우선 옻나무에서 우루시올의 추출을 위하여 나무는 soxhlet의 방법으로, 옻나무 추출물은 liquid-liquid extraction (LLE)의 방법을 이용하여 각각의 우루시올을 추출하였으며, 추출한 각 성분들은 high performance liquid chromatography/ultraviolet & visible detector system (HPLC/UV-Vis)에 먼저 적용하여 분리의 최적 조건을 찾았다. 그리고 각 성분에 대한 정확한 분석을 위하여 reverse phase liquid chromatography on-line electro spray ionization mass spectrometer (LC-MS/MS)를 이용하였으며 이를 바탕으로 분자량에 따른 성분 확인과 함량을 연구하였다. 이동상의 조건으로는 methanol : 0.1% formic acid : DDW를 929 : 1 : 70의 부피비로 사용하여 최적의 분리 조건을 얻었다. 이러한 LC의 조건으로 다시 LC-MS/MS에 적용하여 MRM의 방식으로 각각의 함량을 구할 수 있었다. 분자량에 따라 총 4종류의 우루시올 동종체들이 존재를 확인하였다. 본 연구를 통하여 한국산 옻나무 추출물의 경우 외국산 옻나무의 것 보다 곁사슬에 이중결합이 많은 우루시올 동종체의 함량이 많이 존재하며 그 전체적 비율이 높은 것으로 밝혀졌다.

• 환경위생공학
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• 제21권1호
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• pp.35-43
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• 2006

Formaldehyde is important because of their irritant and toxic properties, mutagenicity and carcinogenicity. In this study, liquid chromatography-mass spectrometry (LC-MS) is used for the analysis of formaldehyde after derivatization with 2,4-dinitrophenylhydrazine (DNPH) cartridge. Analytical parameters such as linearity, repeatability and minimum detection limit were evaluated. The linearity ($r^2$) was 0.9997 when analyte concentration ranges from 25 to $200{\mu}g/l$. The relative standard deviation (%RSD) was 1.25 % for concentration of $200{\mu}g/l$. The minimum detection limit (MDL) was 0.73 ppbv. It was shown that LC-MS method has a great potential for formaldehyde analysis. The results of formaldehyde from the survey of Ban-Woll and Shi-Hwa Industrial Complex samples, the highest level was 6.20, 3.93 ppb, respectively. The highest emission level of formaldehyde at chemical plants in the Ban-Woll' Shi-Hwa Industrial Complex was 5421.25 ppb.

• 분석과학
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• 제15권6호
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• pp.574-579
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• 2002

탄수화물 형태의 당뇨치료제인 acarbose 및 그 대사체를 LC/MS를 사용하는 간편하고 감도 좋은 분석방법을 개발하였다. 혈장시료를 주사기 필터로 거른후 다른 시료전처리과정 없이 LC/MS에 직접 주입하여 분석하였다. Acarbose에 대한 검정곡선은 $0.1{\sim}10{\mu}g/m{\ell}$ 농도범위에서 $r^2=0.9963$의 선형성을 나타내었다. ${\alpha}$-Amylase와 ${\beta}$-amylase를 사용한 in vitro 배양 시험을 통해서 생성된 대사체 component-I과 component-II도 정성적으로 확인 가능하였다. 이러한 LC/MS 분석법은 acarbose의 약동력학적 연구는 물론이며 다른 탄수화물 형태 약물의 연구에도 활용이 가능할 것이다.

• 한국물환경학회지
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• 제25권5호
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• pp.720-726
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• 2009

We investigated the most effective pre-treatment processes and LC/MS/MS condition for microcystins analysis. With a step-by-step pre-treatment, efficiencies of several established methods were compared. At the level of cell burst, sonication method was found to be the most efficient. As a mycrocystins first extraction solvent, 5% acetic acid showed the highest efficiency. An isolation and recovery rate of mycrocystins of ODS Sep-Pak $C_{18}$ cartridge was higher than HLB SPE cartridge. As a final elution solvent from cartridge, 100% MeOH had a better efficiency than others. Using a LC/MS/MS, effective analytical methods were established. C18 reverse column was used and gradient elution was performed with using acetonitrile, 0.1% formic acid as a mobile phase. We analysed to 0.8 mL/min flow rate fit to the $5{\mu}m$ particle size column and $55^{\circ}C$ housing temperature. The validity of established analytical method was evaluated that MDL as average $0.050{\pm}0.014{\mu}g/L$ and LOQ as average $0.160{\pm}0.045{\mu}g/L$ had a good sensitivity over 40 magnification rather than $2{\mu}g/L$ detection limit of HPLC.

• 대한화학회지
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• 제55권4호
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• pp.626-632
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• 2011

폭심(phoxim)은 널리 사용되고 있는 구충제인 동물용의약품이다. 본 논문에서는 소와 돼지 근육에 잔류하는 폭심을 분석하기 위해서, 실리카 고체상과 아세토니트릴을 사용하여 추출/정제하였다. 분석을 위해서 LC/ESI-MS/MS 방법이 사용되었다. HPLC에서 $C_{18}$ 컬럼($2.1{\times}100\;mm$, $3.5\;{\mu}m$)이 사용되었으며, 이동상으로는 0.1% formic acid와 물이 사용되었다. 소(0.0048~2.0 mg/kg)와 돼지(0.0055~2.0 mg/kg)에 소량첨가하여 얻은 검정곡선은 좋은 직선성($r^2$=0.995)을 나타내었다. 소와 돼지의 매트릭스에 대해서 0.0048~0.2 mg/kg범위에서 68.2~106.9%의 정확도를 나타내었으며, LOD는 0.0014~0.0017 mg/kg, LOQ는 0.0048~0.0055 mg/kg범위에 있었으며, 11.2%의 상대표준편차를 나타내었다.

• 한국수산과학회지
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• 제54권4호
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• pp.404-410
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• 2021

Although, mouse bioassay for the monitoring of azaspiracids (AZAs) toxins in shellfish has been used previously, the reported method has low sensitivity and it is time-consuming. Recently, there is an interest in the quantitative analysis of AZAs using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The purpose of this study is to verify the simultaneous analysis of AZAs in shellfish and tunicate in Korea using LC-MS/MS. To validate the method, linearity, limit of detection (LOD), limit of quantification (LOQ), precision, accuracy, and repeatability were determined. All standard compounds were analyzed within 7 min. The correlation coefficients (R²) of the standard solution was higher than 0.9995 (within the range of 0.8-10.0 ㎍/L). The LODs and LOQs of AZAs in shellfish were 0.08-0.16 ㎍/kg and 0.23-0.50 ㎍/kg, respectively. The accuracy and precision of the method for determining AZAs in shellfish were 87.1-93.0% and 1.23-4.91%, respectively. Consequently, the verified LC-MS/MS method is suitable to analyze AZAs in shellfish and tunicates in Korea.

• Mass Spectrometry Letters
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• 제13권3호
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• pp.58-83
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• 2022

We developed analytical methods using high performance chromatography (HPLC) and liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous determination of 80 unapproved compounds in dietary supplements. The target compounds for analysis were unapproved ingredients (e.g., pharmaceuticals) that have potential adverse effects on consumers owing to accidental misuse, overuse, and interaction with other medication in dietary supplement. Two analytical methods were tested to identify the optimal validation results according to AOAC guideline. As a result, limit of quantification (LOQ) was 0.14-0.5 ㎍ mL^-1; linearity (r²) was ≥ 0.99; accuracy (expressed as recovery) was 78.9-114%; precision (relative standard deviation) was ≤ 4.28% in the HPLC method. In the LC-MS/MS method, LOQ was 0.01-2 ng mL^-1, linearity (r²) was ≥0.98, accuracy was 71.7-119%; precision was ≤ 12.5%. The developed methods were applied to 51 dietary supplements collected from 2019 to 2021 through MFDS alert system. Based on our previous monitoring study, major compounds were icariin, sibutramine, yohimbine, sildenafil, tadalafil, sennosides (A, B), cascarosides (A, B, C, D), and phenolphthalein. In this study, we re-analyzed samples of detected compounds, and evaluated the statistical difference using Bland-Altman analysis to compare two analytical approaches between HPLC and LC-MS/MS. These results showed a good agreement between two methods that can be used to monitor the unapproved ingredients in dietary supplements. The developed two methods are complementarily suitable for monitoring the adulteration of 80 unapproved compounds in dietary supplements.

• 농약과학회지
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• 제18권4호
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• pp.296-313
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• 2014

토양환경 중 잔류농약 동시분석을 위해 124종의 농약을 대상으로 QuEChERS 전처리와 LC-MS-MS를 이용한 분석법을 개발하고자 하였다. QuEChERS 전처리 과정은 토양시료에 0.2N $NH_4Cl$ 용액 침지하고 1% acetic acid 포함 acetonitrile 용매로 추출 후 $MgSO_4$ 및 NaOAc로 salting out하고 PSA 50 mg, $C_{18}$ 50 mg, $MgSO_4$ 150 mg를 이용해 정제하였다. 분석법의 검증을 위해 양토 및 사양토 두 토양에서 0.005, 0.01, 0.02, 0.1 mg/kg 4수준으로 처리 후 회수율 실험을 실시하였다. 회수율 실험결과 Benfuracarb, Ethiofencarb, Pymetrozine, Pyrethrin 성분을 제외하고 나머지 성분들은 사양토와 양토 모두 70~120%의 적정 회수율을 나타내었으며, 상대표준편차도 20% 이내를 양호한 결과를 나타내었다. 따라서 QuEChERS 전처리 및 LC-MS를 이용한 분석법은 토양 중 잔류농약 다성분동시분석에 적용이 가능할 것으로 판단되었다.