• Journal of Ginseng Research
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• 제40권3호
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• pp.220-228
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• 2016

Background: Among the various ginseng strains, Shizhu ginseng is endemic to China, mainly distributed in Kuandian Manchu Autonomous County (Liaoning Province, China); however, not much is known about the compounds (especially saponins) in Shizhu ginseng. Methods: A rapid, sensitive, and reliable ultra-high performance liquid chromatography coupled with MS/MS (UHPLC-MS/MS) method was developed to separate and identify saponins in Shizhu ginseng. Results: The separation was carried out on a Waters ACQUITY UPLC BEH $C_{18}$ column ($100mm{\times}2.1mm$, $1.7{\mu}m$) with acetonitrile and 0.1% formic acid aqueous solution as the mobile phase under a gradient elution at $40^{\circ}C$. The detection was performed on a Micromass Quattro Micro API mass spectrometer equipped with electrospray ionization source in both positive and negative modes. Under the optimized conditions, a total of 31 saponins were identified or tentatively characterized by comparing retention time and MS data with related literatures and reference substances. Conclusion: The developed UHPLC-MS/MS method was suitable for identifying and characterizing the chemical constituents in Shizhu ginseng, which provided a helpful chemical basis for further research on Shizhu ginseng.

• 한국식품저장유통학회지
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• 제23권7호
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• pp.1004-1011
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• 2016

본 연구에서는 국내산 대추나무의 잎과 열매의 flavonoid 배당체를 조사하기 위하여 선행 연구된 인용문헌을 바탕으로 대추나무, 묏대추나무, 야생대추나무 등 대추나무속(Zizyphus)에 따른 flavonoid의 화학적 정보 수집 및 정리하여 대추나무속의 flavonoid 라이브러리를 제작하였다. 각 flavonoid 개별성분은 UPLC-DAD-QTOF-ESI/MS를 사용하여 분석하였으며 제작된 라이브러리의 정보를 이용하여 국내산 대추나무로부터 총 6종의 flavonoid를 확인하였다. 이를 통하여 국내산 대추나무 잎의 주요 성분은 quercetin 배당체인 rutin임을 확인하였고, 특히 quercetin 3-O-robinobioside 및 isoquercitrin는 구축된 라이브러리를 바탕으로 대추나무 잎에서는 처음 확인된 것을 알 수 있었다. 본 연구와 같이 대추나무속 flavonoid의 화합물 정보를 포함하여 제작한 라이브러리는 선행된 연구와의 차이점 판단을 가능하게 할 것으로 사료된다.

• 분석과학
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• 제32권1호
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• pp.24-34
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• 2019

The safety of food is occasionally questionable, as there have been some reports of products contaminated with illegal adulterants. In this study, the presence of 16 sedative-hypnotics and sleep inducers in dietary supplements was determined by ultra-high-performance liquid chromatography with UV detection (UPLC-UV) and quadruple Orbitrap mass spectrometry (Q-Orbitrap-MS). The UPLC method was validated, providing a linearity (R2) of more than 0.999, and LODs and LOQs that ranged from 0.2 to 0.5 and 0.6 to $1.5{\mu}g\;mL^{-1}$, respectively. The repeatabilities were 0.2-8.4 % (intra-day) and 0.3-4.5 % (inter-day), and the accuracies were 89.0-117.0 % (intra-day) and 87.8-111.9 % (inter-day). The mean recoveries of the spiked samples ranged from 98.7 to 107.3 %. The relative standard deviation (%RSD) of the stability was less than 2.4 %. Using the developed method, one sedative-hypnotic compound, phenobarbital, was detected in one of the nineteen samples tested. In addition, the major characteristic fragment ions of each target compound were confirmed using Q-Orbitrap-MS for higher accuracy. Monitoring the presence of these 16 sedative-hypnotics and sleep inducers in dietary supplements should be pursued in the interest of human health, and the results of this study confirmed that the developed method has value for this application.

• 생약학회지
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• 제50권1호
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• pp.65-71
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• 2019

One of the oriental medicine prescriptions, Sagunja-tang consists of four herbal medicines (Ginseng Radix, Poria Sclerotium, Atractylodis Rhizoma Alba, and Glycyrrhiziae Radix et Rhizoma) and has been used as a medicine to enhance tonify the function of spleen and stomach in Korea. In this study, we conducted simultaneous analysis of the 9 marker components, liquiritin apioside, liquiritin, ginsenoside Rg1, liquiritigenin, ginsenoside Rb1, glycyrrhizin, atractylenolide III, atractylenolide II, and atractylenolide I in Sagunja-tang using a liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS/MS). Marker compounds were separated on a Waters Acquity UPLC BEH $C_{18}$ analytical column ($2.1{\times}100mm$, 1.7 mm) and the column was maintained at $45^{\circ}C$. The mobile phase consists of 0.1% (v/v) aqueous formic acid and acetonitrile with gradient condition. The LC-MS analysis was performed using a Waters ACQUITY TQD LC-MS/MS system with multiple reaction monitoring (MRM) method in the positive and negative modes. The calibration curves of the nine marker components showed good linearity with coefficient of determination ${\geq}0.9984$ within tested range. The limits of detection and limits of quantification values were 0.27-2.42 ng/mL and 0.81-7.27 ng/mL, respectively. The concentrations of tested 9 analytes in the lyophilized Sagunja-tang sample using the established LC-ESI-MS/MS MRM method were detected up to 16.593 mg/g. These results can be useful as a basic data for the quality control of an oriental medicine prescriptions.

• Journal of Applied Biological Chemistry
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• 제64권3호
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• pp.245-251
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• 2021

더덕(Codonopsis lanceolata)은 주로 한국, 중국 등 동아시아 지역에 재배되고 있으며, 더덕의 뿌리는 기침, 기관지염, 천식, 결핵, 소화 불량의 증상을 치료하기 위한 기능성 식품 및 전통 의학으로 사용되어져 왔다. 보고된 바에 의하면 phenylpropanoids, polyacetylenes, saponins, flavonoids와 같은 다양한 식물 천연물 성분들이 항비만, 항염, 항암, 항산화, 항미생물 활성과 같은 약리학적 작용에 관여한다고 보고되어 있다. MS기반 대사체학 분석을 이용한 주산지의 마커 성분을 선정하는 것은 다른 지역에서 재배된 약용 식물의 안전성뿐만 아니라 화학적 조성과 생물학적 효능의 변화와도 관련이 있기 때문에 부작용 없이 더덕의 유익한 효과만을 보장하는데 중요하다. 본 연구에서는 국내산 더덕의 주산지 특성을 구별하기 위해 UPLC-QTOF-MS를 기반으로 하는 대사체 프로파일링과 다변량 통계분석 기법인 PCA 분석을 수행하여 판별모델을 확립하였다. 그 결과 인제(강원도), 횡성(강원도), 무주(전라북도)의 3개 그룹이 PCA와 loading plot 분석결과 tangshenoside I, lancemaside A, lancemaside G는 더덕 주산지를 구별하기 위한 잠재적 대사체 마커들로 제안하였다.

• 약학회지
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• 제60권2호
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• pp.64-72
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• 2016

Jakyakgamcho-tang is a well-known traditional herbal medicine and has been used for the treatment of mainly pains in oriental medicine. In this study, analytical method for the quantitative determination of the eleven marker components, gallic acid (1), oxypaeoniflorin (2), paeoniflorin (3), albiflorin (4), liquiritin (5), isoliquiritin (6), ononin (7), liquiritigenin (8), benzoylpaeoniflorin (9), paeonol (10), and glycyrrhizin (11) in Jakyakgamcho-tang decoction was performed using an ultra-performance liquid chromatography-electrospray ionization-mass spectrometer. The analytical column for separation of the compounds 1~11 was used an UPLC BEH $C_{18}$ ($100{\times}2.1mm$, $1.7{\mu}m$) column and column oven temperature was maintained at $45^{\circ}C$. The mobile phase consisted of 0.1% (v/v) aqueous formic acid (A) and acetonitrile (B) by gradient elution. The flow rate was 0.3 ml/min and injection volume was $2.0{\mu}l$. Correlation coefficient in the calibration curves of the compounds 1~11 were showed a good linearity with more than 0.99. The limit of detection and limit of quantification values of the compounds 1~13 were detected in the ranges 0.06~18.43 ng/ml and 0.18~58.29 ng/ml, respectively. Among the compounds 1~11, the compounds 10 were not detected in this sample, while the ten compounds, 1~9 and 11, were detected $44.05{\sim}19,289.05{\mu}g/g$ in Jakyakgamcho-tang extract.

• Journal of Applied Biological Chemistry
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• 제62권1호
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• pp.31-38
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• 2019

Scutellaria baicalensis Georgi (Scutellariae Radix)는 이뇨제, 고지혈증, 항박테리아, 항알레르기, 항염증제 및 항암제와 같은 건강보조식 및 전통 생약으로도 널리 사용되어 왔다. 본 연구에서 복잡한 S. baicalensis 추출물에서 지표 물질 또는 유효화합물들을 분리하는 것은 신원 확인 및 생리활성 평가를 위한 필수적인 단계다. 8개의 성분들로 구성된 타겟 분획물을 두개의 gradient elution를 사용하여 고성능 액체 크로마토 그래피에서 분석하였다. 중압 액체크로마토그래피 및 개방형칼럼으로 분취를 시뮬레이션함으로 예비실험에서 충분히 분리가 되도록 용리 조건을 결정할 수 있었다. 최적 분취방법으로 확보된 표준유효분획물로부터 8개의 지표성분들이 포함된 것을 확인하였다. 또한, 분획물은 UPLC-QTof-MS 비교 분석으로 MS, UV, HRESIMS 결과를 확인할 수 있었다. 따라서, 스케일 업 실험법은 S. baicalensis 추출물에 성공적으로 적용될 수 있었다.

• 한국환경보건학회지
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• 제48권1호
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• pp.36-43
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• 2022

Background: Preservatives are used to prevent product deterioration in modeling clay. Parabens, a representative preservative, have been found to be endocrine disruptors and cause skin irritation and allergic reactions. Isothiazolinone preservatives can be irritating to the skin, respiratory tract, and eyes. Thorough investigation and regulation of clay are necessary because clay is marketed to children, who are more sensitive to the toxic effect of chemicals. Objectives: In this study, the presence of 16 preservatives was analyzed in modeling clay and the results were compared with current standards. Methods: A total of 200 samples were collected from 28 children's clay products sold in South Korea (13 from Korea and 15 imported from overseas). Twelve preservatives, such as parabens, were analyzed using high-performance liquid chromatography (HPLC). Isothiazolinone preservatives (chloromethylisothiazolinone; CMIT, methylisothiazolinone; MIT, octylisothiazolinone; OIT, and benzisothiazolinone; BIT) were analyzed using ultra performance liquid chromatography-tandem mass spectrometery (UPLC-MS/MS). Results: Dehydroacetic acid (DHA) was detected the most in the clays at 51.50% (103 cases) detection; 38 cases (median 190.42 ㎍/g) in Korean products and 65 cases (median 169.62 ㎍/g) in Chinese products. CMIT, which is prohibited in Korea, was detected in 14 (median 16.28 ㎍/g) Chinese products. OIT, which has a chemical structure similar to CMIT was found in 28 (median 68.38 ㎍/g) samples in Korean products. Conclusions: The use of CMIT and MIT in children's products is prohibited in Korea and the European Union (EU). The detection of CMIT in Chinese clay products suggests that management is necessary for imported products. It is necessary to review the safety and regulatory status for OIT because OIT was used as a substitute for CMIT and MIT in Korean products.

• 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.

• Journal of Applied Biological Chemistry
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• 제63권4호
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• pp.393-399
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• 2020

방풍(Saposhnikoviae Radix, SR) 과 식방풍(Peucedani Japonici Radix, PR)은 각각 다른 기원식물을 가지며 속과 종이 다르지만 한국, 중국, 및 일본에서 대표적인 전통 한약재로 오랫동안 혼용되어 사용되었다. 본 연구에서는 방풍과 식방풍의 판별 마커를 확인하기 위하여 UPLC-QTOF/MS를 이용한 대사체 프로파일링 및 다변량 통계분석을 진행하였다. 그 결과, 5-O-methylvisammioside와 peucedanol을 각각 방풍과 식방풍의 지표성분으로 선정하였으며, UPLC를 이용하여 분석법을 검증하였다. 제안된 방풍 및 식방풍의 지표성분에 대한 분석법 검증은 방풍과 식방풍의 분류와 품질 평가 및 성분 검증을 위한 효과적인 방법이 될 것으로 기대된다.