• Mass Spectrometry Letters
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• 제1권1호
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• pp.29-32
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• 2010

Cross reacting antibodies can cause an overestimation of the results of immunoassays. Therefore, alternative methods are needed for the accurate quantification of steroids. Gas chromatography combined with isotope-dilution mass spectrometry (GC-IDMS) is developed to quantify urinary active androgens, testosterone, epitestosterone and dihydrotestosterone, which are clinically relevant androgens to both hair-loss and prostate diseases. The method devised involves enzymatic hydrolysis with $\beta$-glucuronidase, solid-phase extraction, liquid-liquid extraction using methyl tert-butyl ether and subsequent conversion to pentafluorophenyldimethylsilyl-trimethylsilyl (flophemesyl-TMS) derivatives for sensitive and selective analysis in selected-ion monitoring mode. Flophemesyl-TMS derivatization not only eliminates matrix interference but also has a good peak resolution within a 6 min-run. A selective and sensitive GC technique with flophemesyl-TMS derivatives also allows accurate quantitative analysis of three active androgens when combined with IDMS. The limit of quantification of the three analytes was <50 pg/mL, and extraction recoveries ranged from 91.9 to 102.1%. The precision and accuracy were 1.2~6.5% and 89.0~106.7%, respectively. This GC-IDMS method can be useful for evaluating the drug efficacy and monitoring the biological processes responsible for male-pattern baldness and prostate diseases.

• 약학회지
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• 제51권3호
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• pp.206-213
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• 2007

Recently estimating the uncertainty of an analytical result has become an essential part of quantitative analysis. This study describes the uncertainty of the measurement for the determination of methamphetamine and its major metabolite amphetamine in human hair, The method consists of washing, drying, weighing, incubation and extraction with methanolic HCI solution, clean-up, trifluoroacetyl derivatization, and qualification/quantification of residues by gas chromatography/mass spectrometry (GC/MS). Traceability of measurement was established through traceable standards and calibrated volumetric equipment and measuring instruments. Measurement uncertainty associated with each analyte in real samples was estimated using quality control (QC) data. The main source of combined standard uncertainty comprised two components, which are uncertainties associated with calibration linearity and variations in QC, while those associated with preparation of analytical standards and sample weighing were not so important considering the degree of contribution. Relative combined standard uncertainties associated with the described method ranged for individual analytes from 4.99 to5.03%.

• Bulletin of the Korean Chemical Society
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• 제25권6호
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• pp.900-906
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• 2004

An RPLC-postcolumn detection method has been developed for the fluorimetric determination of dichloroacetamide (DCAD) in water. After ammonia and DCAD were separated on a $C_{18}$ nonpolar stationary phase with 2.5% methanol-0.02 M phosphate buffer at pH 3, the column eluant was reacted with post column reagents, o-phthaldialdehyde (OPA) and sulfite ion at pH 11.5, to produce a highly fluorescent isoindole fluorophore, which was measured with a fluorescence detector ( ${\lambda}_{ex}$ = 363 nm, ${\lambda}_{em}$ = 425 nm). With the optimized conditions for RPLC and the postcolumn derivatization, the calibration curve was found to be linear in the concentration ranges of 0.5 and 20 ${\mu}$M for DCAD, and the detection limit for DCAD was 0.18 ${\mu}$M (23${\mu}$g/L). This corresponded to 18 pmol per 100 ${\mu}$L injection volume for a signal-to-noise ratio of 3, and the repeatability and reproducibility of this method were 1.0% and 2.5% for five replicate analyzes of 2 ${\mu}$M DCAD, respectively. The degradation yields DCAD to ammonia were 94 and 99%, and the percent recoveries of DCAD from 4 and 6 ${\mu}$M DCAD-spiked tap water were shown mean more than 97%.

• 고려인삼학회:학술대회논문집
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• 고려인삼학회 1980년도 학술대회지
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• pp.59-69
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• 1980

A new HPLC-method for separation and quantitative determination of ginsenosides in Panax ginseng, Panax quinquefolium and in pharmaceutical drug preparations is elaborated. A reversed-phase-system with ${\mu}Bondapak\;C_{18}$ column (3.9 mm $I.D.{\times}30\;cm$) using acetonitrile-water (30:70) 2 ml/min and acetonitrile-water (18:82) 4 ml/min is suitable for the base-line separation of $Rb_1,\;Rb_2,\;Rc,\;Rd,\;Rf,\;Rg_2,\;respectively\;Re,\;Rg_1$ in 30 minutes. The ginsenosides are directly detected at 203 nm (without derivatization) with the LC-55 or LC-75 spectrophotometer (Perkin-Elmer) at $100\%$ transmission. Detection limit is 300 ng at a signal-to-noise ratio of 10:1. The ginsenosides-peak identification is carried out with HPTLC (high performance thin layer chromatography), with MIR-IR (multiple internal reflection-IR-spectros-copy) and with FD-MS (field desorption mass spectrometry). The calibration curve of each ginsenoside has a correlation coefficient very near to 1. Relative standard deviation for quantitative determinations depends upon the amount of ginsenosides and is approximately 1\%$ for ginsenoside contents of 1\%$. This method is adaptable for routine analysis in quality control laboratories.

• 한국수산과학회지
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• 제55권2호
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• pp.218-223
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• 2022

Cholesterol is an essential component for maintaining health; however, excessive consumption can lead to diseases. Thus, continuous monitoring of cholesterol content is important in food research. The cholesterol analysis method used in Korea follows the Korean Food Standards Codex. As this method uses gas chromatography, derivatization of the sample is required, and analysis time is more than 30 min. Kim developed a new method using liquid chromatography; however saponification by the non-heat saponification method is insufficient. To address these limitations, a new cholesterol analysis method was developed and verified. The correlation coefficients for the cholesterol standard (STD) were maintained above 0.99. The limit of detection and limit of quantitation of cholesterol STD were 2.41 ㎍/mL and 7.31 ㎍/mL, respectively. The accuracies for cholesterol were 92.21-99.02%. The developed analytical method was also verified using three standard reference materials, and their accuracies were 93.71-97.09%. In addition, the cholesterol content of fishes was analyzed, and the values were compared with those recorded by the United States Department of Agriculture. Our results suggest that this method could be used as a new analytical method for cholesterol in seafood.

• 대한임상검사과학회지
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• 제37권1호
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• pp.22-26
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• 2005

Total homocysteine is now considered a risk factor for cardiovascular diseases. I increased interest has led to a multitude of studies requiring the determination of total homocysteine in conjunction with other factor. There are various methods for measuring total homocysteine, including HPLC, FPIA, GC-MS and LC-MS/MS. The most recent method for measuring total homocysteine uses a deuterium-labelled internal standard and tandem mass spectrometry. This development requires no derivatization and therefore leads to an increase in sample throughput compared to other techniques. We have evaluated the method for homocysteine by the LC-MS/MS method, and the correlation between the FPIA method and the LC-MS/MS method. The standard curve (0, 5, 10, 20, 50, 100 uM) was linear over the range examined (up to 100 uM). The lower limit of quantification (CV < 10 %) was 0.5 uM/L and the lower limit of detection (S/N >3) was 0.1 uM/L. Intra-assay variation and inter-assay variation were both <6 %. The comparision study for homocysteine concentration showed good correlation (r=0.9684) between the FPIA method and LC-MS/MS methods. Our conclusion is that the method showed relatively good precision, and was rapid and accurate.

• Mass Spectrometry Letters
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• 제4권4호
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• pp.75-78
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• 2013

A gas chromatography/mass spectrometric (GC/MS) method was developed as a candidate reference method for the accurate determination of essential fatty acids (linoleic acid, ${\alpha}$- and ${\gamma}$-linolenic acids) in food supplemental oil products. Samples were spiked with three internal standards (stearic acid-$d_{35}$, $^{13}C_{18}$-linoleic acid, and $^{13}C_{18}$-${\alpha}$-linolenic acid). Samples were then subject to saponification, derivatization for methylation, and extraction by organic solvent. For GC/MS measurement, an Agilent HP-88 column, designed for the separation of fatty acid methyl esters, was selected after comparing with other columns as it provided better separation for target analytes. Target analytes and internal standards were detected by selected ion monitoring of molecular ions of their methyl ester forms. The GC/MS method was applied for the measurement of three botanical oils in NIST SRM 3274 (borage oil, evening primrose oil, and flax oil), and measurement results agreed with the certified values. Measurement results for target analytes which have corresponding isotope-labeled analogues as internal standard were calculated based on isotope dilution mass spectrometry (IDMS) approach, and compared with results calculated by using the other two internal standards. Results from the IDMS approach and the typical internal standard approach were in good agreement within their measurement uncertainties. It proves that the developed GC/MS method can provide similar metrological quality with IDMS methods for the measurement of fatty acids in natural oil samples if a proper fatty acid is used as an internal standard.

• 분석과학
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• 제7권3호
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• pp.395-402
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• 1994

본 연구에서는 두 종류의 기존 HPLC 베노밀 분석법 및 한 종류의 새로이 설정한 GC PFB 유도체화 베노밀 분석법을 도입하여 시중에 유통되는 국산 및 수입작물을 수거한 후 그 잔류도를 검색함과 동시에 각 분석법의 정확성, 정밀도, 회수율, 그리고 감도 등을 비교 평가하였다. 그 결과 GC PFB 유도체화분석법의 경우 회수율 및 검출 한계가 각각 95% 이상, $0.001{\mu}g/g$이었다. 그리고 각종 작물의 분석시 기존의 HPLC법의 경우 베노밀의 peak가 나타나는 retention time 시간대에 시료의 성분에 의한 peak도 동시에 나타날 수 있는 확률이 높아 오검출되는 사례가 많았으나 GC PFB 유도체화분석법은 베노밀을 유도체화한 후 GC에서 분석함으로써 오검출 판정결과를 보이는 시료는 없었다.

• 한국식품과학회지
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• 제39권4호
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• pp.360-365
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• 2007

간장 중 3-MCPD 분석을 위한 HFBI, PBA, BSTFA 및 MBTFA를 사용한 유도체화 방법 및 시료 정제를 위한 흡착제, 용출용매 및 Surrogate, 내부표준물질 등을 검증한 결과 MBTFA를 이용한 acylation 방법을 제외한 나머지 세가지 유도체화 방법 모두 0.01 mg/kg 이하의 검출한계를 확인하였으며 정량한계(검출한계 ${\times}$3배)를 고려하더라도 현재의 국내 0.3 mg/kg 기준을 분석하는데 문제가 없는 것으로 판단되었으나 유럽의 허용치 0.02 mg/kg을 분석하기 위해서는 PBA방법이나 BSTFA를 사용한 유도체화 방법의 경우 최종 시료액을 약 5배 이상 농축할 필요가 있다. 한편, 유도체화를 위한 반응조건으로 가열시간 및 온도는 HFBI와 BSTFA를 사용하는 경우 $70^{\circ}C$에서 각각 30 및 60분 그리고 PBA는 첨가 직후부터 가열 없이 반응이 완결되는 것으로 나타났다. 흡착제는 Extrelut20 혹은 Florisil 이 가장 적합한 것으로 확인되었으며, 흡착제로부터의 3-MCPD 용출용매로는 ethyl acetate가 상대적으로 높은 추출능을 보여 주었다. 또한 고가의 3-MCPD 중수 소치환 동위원소 surrogate 물질을 대체하기 위한 surrogate 표준물질로는 1,2-butanediol이 그리고 내부표준물질로는 1,2-dibromo-3-chloropropane이 가장 적합한 것으로 확인하였다.

• 한국초지조사료학회지
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• 제35권3호
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• pp.257-263
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• 2015

This study was conducted to assess the potential of using NIRS to accurately determine the chemical composition and fermentation parameters in fresh coarse sorghum and sudangrass silage. Near Infrared Spectroscopy (NIRS) has been increasingly used as a rapid and accurate method to analyze the quality of cereals and dried animal forage. However, silage analysis by NIRS has a limitation in analyzing dried and ground samples in farm-scale applications because the fermentative products are lost during the drying process. Fresh coarse silage samples were scanned at 1 nm intervals over the wavelength range of 680~2500 nm, and the optical data were obtained as log 1/Reflectance (log 1/R). The spectral data were regressed, using partial least squares (PLS) multivariate analysis in conjunction with first and second order derivatization, with a scatter correction procedure (standard normal variate and detrend (SNV&D)) to reduce the effect of extraneous noise. The optimum calibrations were selected on the basis of minimizing the standard error of cross validation (SECV). The results of this study showed that NIRS predicted the chemical constituents with a high degree of accuracy (i.e. the correlation coefficient of cross validation ($R^2{_{cv}}$) ranged from 0.86~0.96), except for crude ash which had an $R^2{_{cv}}$ of 0.68. Comparison of the mathematical treatments for raw spectra showed that the second-order derivatization procedure produced the best result for all the treatments, except for neutral detergent fiber (NDF). The best mathematical treatment for moisture, acid detergent fiber (ADF), crude protein (CP) and pH was 2,16,16 respectively while the best mathematical treatment for crude ash, lactic acid and total acid was 2,8,8 respectively. The calibrations of fermentation products produced poorer calibrations (RPD < 2.5) with acetic and butyric acid. The pH, lactic acid and total acids were predicted with considerable accuracy at $R^2{_{cv}}$ 0.72~0.77. This study indicated that NIRS calibrations based on fresh coarse sorghum and sudangrass silage spectra have the capability of assessing the forage quality control