• 분석과학
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• 제32권6호
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• pp.252-261
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• 2019

피롤리지딘 알칼로이드(Pyrrolizidine alkaloids, PAs)는 식물이 포식자로부터 자신을 방어하기 위해 생산하는 2차 대사산물이다. 현재까지 약 6,000 여종 이상의 식물에서 660 여개의 피롤리지딘 알칼로이드가 확인되었으며 주로 국화과, 지치과, 콩과 식물에 분포한다. 본 연구에서는 UPLC-MS/MS를 이용하여 벌꿀 속 자연독소의 일종인 피롤리지딘 알칼로이드 7 종에 대한 분석방법을 확립하고 유통중인 벌꿀제품 84건에 대하여 PAs 함유량을 모니터링하였다. 정량은 전자분무이온화 과정에서 벌꿀에 대한 matrix effect를 줄이기 위해 matrix-matched 검량선을 사용하였다. 직선성은 R² ≥ 0.998, PAs 7 종에 대한 회수율은 81-108 % 수준이었다. 7종 동시분석법으로 국내 유통중인 벌꿀 84건을 검사한 결과, 7.1 % (6/84건)의 검출률을 보였으며 검출량은 평균적으로 47.19 ㎍/kg이었다. 또한 검출된 PA 성분은 주로 Lycopsamine과 Echimidine으로 확인되었으며 1.76-202.1 ㎍/kg의 검출범위를 나타내었다.

• Journal of Ginseng Research
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• 제40권4호
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• pp.382-394
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• 2016

Background: Ginsenosides are the characteristic and principal components which manifest a variety of the biological and pharmacological activities of the roots and rhizomes of Panax ginseng (GRR). This study was carried out to qualitatively and quantitatively determine the ginsenosides in the cultivated and forest GRR. Methods: A rapid and sensitive ultra-high-performance liquid chromatography coupled with diode-array detector and quadrupole/time of flight tandem mass spectrometry (UPLC-DAD-QTOF-MS/MS) was applied to the qualitative analysis of ginsenosides and a 4000 QTRAP triple quadrupole tandem mass spectrometer (HPLC-ESI-MS) was applied to quantitative analysis of 19 ginsenosides. Results: In the qualitative analysis, all ingredients were separated in 10 min. A total of 131 ginsenosides were detected in cultivated and forest GRR. The method for the quantitative determination was validated for linearity, precision, and limits of detection and quantification. 19 representative ginsenosides were quantitated. The total content of all 19 ginsenosides in the forest GRR were much higher than those in the cultivated GRR, and were increased with the growing ages. Conclusion: This newly developed analysis method could be applied to the quality assessment of GRR as well as the distinction between cultivated and forest GRR.

• Journal of Ginseng Research
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• 제40권4호
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• pp.344-350
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• 2016

Background: Mountain-cultivated ginseng (MCG) and cultivated ginseng (CG) both belong to Panax ginseng and have similar ingredients. However, their pharmacological activities are different due to their significantly different growth environments. Methods: An ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS/MS)-based approach was developed to distinguish MCG and CG. Multivariate statistical methods, such as principal component analysis and supervised orthogonal partial-least-squares discrimination analysis were used to select the influential components. Results: Under optimized UPLC-QTOF-MS/MS conditions, 40 ginsenosides in both MCG and CG were unambiguously identified and tentatively assigned. The results showed that the characteristic components of CG and MCG included ginsenoside Ra3/isomer, gypenoside XVII, quinquenoside R1, ginsenoside Ra7, notoginsenoside Fe, ginsenoside Ra2, ginsenoside Rs6/Rs7, malonyl ginsenoside Rc, malonyl ginsenoside Rb1, malonyl ginsenoside Rb2, palmitoleic acid, and ethyl linoleate. The malony ginsenosides are abundant in CG, but higher levels of the minor ginsenosides were detected in MCG. Conclusion: This is the first time that the differences between CG and MCG have been observed systematically at the chemical level. Our results suggested that using the identified characteristic components as chemical markers to identify different ginseng products is effective and viable.

• 원예과학기술지
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• 제33권4호
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• pp.470-478
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• 2015

본 연구는 국내에서 재배중인 '개량머루', '거봉', '홍이슬' 품종의 anthocyanin 조성을 UPLC-ESI-MS/MS를 이용하여 조사하였다. '개량머루'는 착색에 불량하게 작용하는 기상 조건에서도 착색이 우수한 흑포도 품종이고, '거봉'과 '홍이슬'은 교잡종 포도로 각각 검정색과 분홍색 과피를 갖고 있다. 과피에서 추출된 anthocyanin의 조성은 UPLC-ESI-MS/MS를 이용하여 분석하였다. 각 품종에서 검출된 anthocyanin은 '개량머루'와 '거봉'에서는 각각 25가지, '홍이슬'에서는 21가지였고, 각 품종에서 검출량이 많았던 anthocyanin은 8(개량머루), 15(거봉), 5(홍이슬)가지였다. 세 품종 모두 mono-glucoside가 di-glucoside보다 많았으며, '개량머루'와 '거봉'은 malvidin이 많았던 반면, '홍이슬'은 cyanidin이 가장 많았다. '개량머루'는 acylated anthocyanin(2.0%)은 거의 존재하지 않았고 '거봉'과 '홍이슬'에서는 p-coumaric acid의 acylation이 가장 많았다. Cyanidin feruloyl glucoside가 '홍이슬'에서만 검출되어 품종 지표로 활용이 가능하였다. 결론적으로 anthocyanin의 조성을 anthocyanidin, 결합된 당의 개수, acylation 및 특정 anthocyanin을 기준으로 분류하여 품종의 특징이 확인되었다. 이러한 품종별 anthocyanin 특성을 이용하여 '개량머루'가 Vitis amurensis 혹은 그 교잡종의 가능성과 '홍이슬'에서 품종 구별의 기준으로 활용 가능성이 확인되었다.

• 농약과학회지
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• 제15권1호
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• pp.15-21
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• 2011

본 연구는 QuEChERS 방법에 기초한 EN15662 buffer 및 dSPE, UPLC-MS/MS플 활용하여 경남지역에서 생산되는 대일 수출용 파프리카 내 neonicotinoid계 농약성분의 잔류성 실태 조사를 위하여 수행하였다. 6종의 neonicotinoid계 농약의 회수율 및 변이계수는 0.05 및 0.5 mg/kg 수준에서 각각 84.0~92.7(${\pm}0.0{\sim}3.8%$)과 95.1~98.9%(${\pm}0.9{\sim}5.2%$)로 나타났다. 분석에 사용된 95시료 중 90.3%에서 농약성분이 검출되었으며, 82.3%에서 2종이상의 농약성분이 검출되었다. 검출된 농약의 농도는 0.01~1.63 mg/kg으로 나타났고, 농약성분 중 dinotefuran 및 imidacloprid가 78.1 및 65.6%의 빈도를 보였다. 6종의 농약 중 thiacloprid가 8.3%로 분석된 농약 중 가장 낮은 빈도를 나타내었다. 그러나 검출된 농약의 경우 모두 한국 및 일본의 잔류허용기준을 초과하지 않는 것으로 나타나, 경남지역 생산 대일 수출용 파프리카의 경우 neonicotinoid 계 농약에 대한 사용이 안전한 수준으로 잘 관리되고 있음을 확인하였다.

• Journal of Ginseng Research
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• 제38권1호
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• pp.59-65
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• 2014

Discriminating between two herbal medicines (Panax ginseng and Panax quinquefolius), with similar chemical and physical properties but different therapeutic effects, is a very serious and difficult problem. Differentiation between two processed ginseng genera is even more difficult because the characteristics of their appearance are very similar. An ultraperformance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-QTOF MS)-based metabolomic technique was applied for the metabolite profiling of 40 processed P. ginseng and processed P. quinquefolius. Currently known biomarkers such as ginsenoside Rf and F11 have been used for the analysis using the UPLC-photodiode array detector. However, this method was not able to fully discriminate between the two processed ginseng genera. Thus, an optimized UPLC-QTOF-based metabolic profiling method was adapted for the analysis and evaluation of two processed ginseng genera. As a result, all known biomarkers were identified by the proposed metabolomics, and additional potential biomarkers were extracted from the huge amounts of global analysis data. Therefore, it is expected that such metabolomics techniques would be widely applied to the ginseng research field.

• 분석과학
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• 제30권4호
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• pp.194-204
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• 2017

Direct injection (DI) and solid phase extraction (SPE) methods for the simultaneous determination of pendimethalin (PDM) and dinoseb (DNS) in environmental water have been optimized using the ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method. The limits of quantification (LOQs) of PDM and DNS were $0.01{\mu}g/L$ using the DI method and $0.0001-0.0002{\mu}g/L$ using the SPE method. The precision by SPE UPLC-MS/MS was less than 11 % for intra-day and inter-day analyses. When the proposed SPE method was used to analyze two analytes in environmental water, PDM was detected in a concentration range of $0.0002-0.011{\mu}g/L$ in 31 samples of the 114 surface water samples, and DNS was detected in a concentration range of $0.0005-0.045{\mu}g/L$ in 17 samples of the 114 surface water samples analyzed. When the DI method was used to analyze target compounds in the same samples, the detected concentrations of the two analytes were within 21% in samples with concentrations above $0.01{\mu}g/L$. The DI UPLC-MS/MS method can thus be used for the routine monitoring of PDM and DNS in environmental water, and the SPE LC-MS/MS method can be used for the determination of the ultra-trace PDM and DNS residues in environmental water.

• 한국자원식물학회:학술대회논문집
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• 한국자원식물학회 2010년도 정기총회 및 춘계학술발표회
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• pp.5-5
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• 2010

Selection of specific medicinal sources as well as bioactive compounds is important for the preparation of medicine and related products with good quality. It is necessary to pay close attention for choosing correct medicinal sources, particularly in case of medicinal plants, because of their diversity, which can affect the quality and efficacy of medicine. Discrimination of plants based on morphological or genetic characteristics has been used as a conventional classification method of pharmaceutical sources so far; however, more need demands more general methods for accurate quality assessment of medicinal plants. In this study, ultra performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC/Q-TOF MS) technique applied to this metabolic profiling is a powerful tool due to its higher sensitivity, resolution, and speed compared to conventional HPLC technique. The metabolite profiling of several medicinal plants including Panax ginseng was carried out using UPLC/Q-TOF MS and total metabolites were then subsequently applied to various statistical tools to compare the patterns. The developed metabolomics tool with UPLC/Q-TOF MS successfully identified and classified the samples tested according to their origins.

• 생약학회지
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• 제49권1호
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• pp.76-83
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• 2018

A traditional herbal formula, Gyeji-tang has been used to treat the early colds, headache, chills, and fever in Asian countries. In this study, we were performed simultaneous determination of the 14 bioactive marker compounds, gallic acid, spinosin, paeoniflorin, albiflorin, liquiritin apioside, liquiritin, 6'''-feruloylspinosin, liquilitigenin, coumarin, cinnmamic acid, benzoylpaeoniflorin, cinnamaldehyde, glycyrrhizin, and 6-gingerol in Gyeji-tang using an ultra-performance liquid chromatography-electrospray ionization-mass spectrometry (UPLC-ESI-MS/MS). Analytical column was used a Waters Acquity UPLC BEH $C_{18}$ analytical column ($2.1{\times}100mm$, $1.7{\mu}m$) and maintained at $45^{\circ}C$ with a flow rate of 0.3 mL/min. The mobile phase consists of 0.1% (v/v) formic acid in water and acetonitrile with gradient elution. The MS analysis was conducted using multiple reaction monitoring in the positive and negative modes by a Waters ACQUITY TQD LC-MS/MS system. The calibration curves of 14 bioactive marker compounds showed linearity with correlation coefficients ${\geq}0.9798$. The limits of detection and quantification values were in the range of 0.11-6.66 ng/mL and 0.34-19.99 ng/mL, respectively. As a result of the analysis using the established LC-MS/MS method, the amounts of tested 14 compounds in the lyophilized Gyeji-tang sample were detected up to $85.7{\mu}g/g$. These results may be useful for quality assessment of a traditional herbal formulas.

• 생약학회지
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• 제49권3호
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• pp.270-277
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• 2018

Pyungwi-san has been used to treat the digestive system diseases, physconia, nausea, anorexia, and dyspepsia in Korea. In this study, an ultra-performance liquid chromatography-electrospray ionization-mass spectrometry (UPLC-ESI-MS/MS) method was optimized for simultaneous determination of the 14 marker components, spinosin, liquiritirn apioside, liquiritin, narirutin, 6'''-feruloylspinosin, hesperidin, liquiritigenin, glycyrrhizin, 6-gingerol, atractylenolide III, honokiol, atractylenolide II, magnolol, and atractylenolide I in Pyungwi-san extract. All analytes were separated on a Waters Acquity UPLC BEH $C_{18}$ analytical column ($2.1{\times}100mm$, $1.7{\mu}m$) with maintained at $45^{\circ}C$. The mobile phase consisted of 0.1% (v/v) aqueous formic acid and acetonitrile. The MS conditions were as follows: capillary voltage 3.3 kV, extractor voltage 3.0 V, RF lens voltage 0.3 V, source temperature $120^{\circ}C$, desolvation temperature $300^{\circ}C$, desolvation gas 600 L/h, cone gas 50 L/h and collision gas 0.14 mL/min. The coefficient of determination of 14 analytes was 0.9989-1.0000. The limits of detection and quantification values of the all analytes were 0.04-2.56 and 0.13-7.69 ng/mL, respectively. As a result of the analysis using the established LC-ESI-MS/MS method, the 5 components, spinosin, 6'''-feruloylspinosin, atractylenolide III, II, and I derived from Zizyphi Fructus and Atractylodis Rhizoma, were not detected in this extract. On the other hand, the 9 components except for the 5 components were 4.15-498.87 mg/kg in lyophilized Pyungwi-san extract. Among these components, glycyrrhizin, marker compound of Glycyrrhizae Radix et Rhizoma, was detected the most amount as a 498.87 mg/kg.