• Title/Summary/Keyword: Weighting Curve

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Simultaneous Determination of Methylphenidate, Amphetamine and their Metabolites in Urine using Direct Injection Liquid Chromatography-Tandem Mass Spectrometry

  • Kwon, Woonyong;Suh, SungIll;In, Moon Kyo;Kim, Jin Young
    • Mass Spectrometry Letters
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    • v.5 no.4
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    • pp.104-109
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    • 2014
  • Nonmedical use of prescription stimulants such as methylphenidate (MPH) and amphetamine (AP) by normal persons has been increased to improve cognitive functions. Due to high potential for their abuse, reliable analytical methods were required to detect these prescription stimulants in biological samples. A direct injection liquid chromatography-tandem mass spectrometric (LC-MS/MS) method was developed and implemented for simultaneous determination of MPH, AP and their metabolites ritalinic acid (RA) and 4-hydroxyamphetamine (HAP) in human urine. Urine sample was centrifuged and the upper layer ($100{\mu}L$) was mixed with $800{\mu}L$ of distilled water and $100{\mu}L$ of internal standards ($0.2{\mu}g/mL$ in methanol). The mixture was then directly injected into the LC-MS/MS system. The mobile phase was composed of 0.2% formic acid in distilled water (A) and acetonitrile (B). Chromatographic separation was performed by using a Capcell Pak MG-II C18 ($150mm{\times}2.0mm$ i.d., $5{\mu}m$, Shiseido) column and all analytes were eluted within 5 min. Linear least-squares regression with a 1/x weighting factor was used to generate a calibration curve and the assay was linear from 20 to 1500 ng/mL (HAP), 40-3000 ng/mL (AP and RA) and 2-150 ng/mL (MPH). The intra- and inter-day precisions were within 16.4%. The intra- and inter-day accuracies ranged from -15.6% to 10.8%. The limits of detection for all the analytes were less than 4.7 ng/mL. The suitability of the method was examined by analyzing urine samples from drug abusers.

Rapid Determination of Caffeine in Forensic Aqueous Sample by Dilute and Shoot LC-MS/MS (시료 희석 직접 주입 LC-MS/MS를 이용한 법화학 수용액 시료 중 카페인 신속 분석)

  • Choi, Yun Jeong;Kim, Hee Seung;In, Moon Kyo;Kim, Jin Young
    • YAKHAK HOEJI
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    • v.60 no.3
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    • pp.112-117
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    • 2016
  • A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for the determination of caffeine in forensic aqueous sample. The centrifuged sample ($100{\mu}l$) was diluted 50-fold with distilled water. The diluted sample ($400{\mu}l$) was then diluted further with $200{\mu}l$ of 0.1% formic acid solution and $400{\mu}l$ of acetonitrile containing 500 ng of caffeine-(3-methyl-$^{13}C_3$) prior to LC-MS/MS analysis. The mobile phase was composed of 0.1% formic acid in distilled water (A) and acetonitrile (B). Chromatographic separation was performed by using a Zorbax SB-C18 ($100mm{\times}2.1mm$ i.d., $3.5{\mu}m$) column and caffeine was eluted within 1.1 min. Linear least-squares regression with a 1/x weighting factor was used to generate a calibration curve with the coefficients of determination ($r^2=0.9983$). The lower limit of quantification was $25ng/ml$ for the analyte. The process efficiency was 98.6~100.1%. Intra- and inter-day precisions were not more than 2.1% and 1.7%, while intra- and inter-day accuracies were ranged from -6.8 to 4.5%, respectively. The suitability of the method was examined by analyzing unknown forensic aqueous samples.

Analysis and Evaluation of Ride Comfort for High Speed Train using Statistical Method according to UIC 513R (UIC 513R에 따른 통계적 방법을 이용한 고속철도 차량의 승차감 분석 및 평가)

  • 김영국;김석원;목진용;김기환;박태원
    • Journal of the Korean Society for Railway
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    • v.7 no.4
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    • pp.332-338
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    • 2004
  • The two projects about the high speed train have been performed in Korea, one project is the commercial run of high speed train(KTX) from Seoul to Busan and the other is the development of original high speed train(HSR 350x). As the successful results, the service run of KTX had been launched on the 1st of April, 2004 and HSR 350x had been fabricated in June, 2002 and has been tested in the Kyoungbu line and Honam line since then. The railway has the track irregularities which cause vibrations, such as rail joints, turnout, level crossing, transition curves and super-elevation ramps, and variations in the track level(z-axis) and the gauge(y-axis). Generally, the ride comfort for railway is evaluated by using the vibrations. In this paper, the ride comfort indices according to mc 513R and ISO 10056 have been reviewed when the high-speed trains are operated on both Kyoungbu line and Honam line. Also, the ride characteristics for KTX and HSR 350x on the high speed line and the conventional line have been analyzed and evaluated. The results show that the high-speed train has no problem from the viewpoint of the comfort ride on the high speed line and the conventional line and the ride index for HSR 350x is same as that for KTX in the high speed(300 km/h).

Determination of methamphetamine and amphetamine enantiomers in human urine by chiral stationary phase liquid chromatography-tandem mass spectrometry

  • Sim, Yeong Eun;Ko, Beom Jun;Kim, Jin Young
    • Analytical Science and Technology
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    • v.32 no.5
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    • pp.163-172
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    • 2019
  • Methamphetamine (MA) is currently the most abused illicit drug in Korea and its major metabolite is amphetamine (AP). As MA exist as two enantiomers with the different pharmacological properties, it is necessary to determine their respective amounts in a sample. Thus a chiral stationary phase liquid chromatography-tandem mass spectrometric (LC-MS/MS) method was developed for identification and quantification of d-MA, l-MA, d-AP, and l-AP in human urine. Urine sample ($200{\mu}L$) was diluted with pure water and purified using solid-phase extraction (SPE) cartridge. A $5-{\mu}L$ aliquot of SPE treated sample solution was injected into LC-MS/MS system. Chiral separation was carried out on the Astec Chirobiotic V2 column with an isocratic elution for each enantiomer. Identification and quantification of enantiomeric MA and AP was performed using multiple reaction monitoring (MRM) detection mode. Linear regression with a $1/x^2$ as the weighting factor was applied to generate a calibration curve. The linear ranges were 25-1000 ng/mL for all compounds. The intra- and inter-day precisions were within 3.6 %, while the intra- and inter-day accuracies ranged from -5.4 % to 11.8 %. The limits of detection were 2.5 ng/mL (d-MA), 3.5 ng/mL (l-MA), 7.5 ng/mL (d-AP), and 7.5 ng/mL (l-AP). Method validation parameters such as selectivity, matrix effect, and stability were evaluated and met acceptance criteria. The applicability of the method was tested by the analysis of genuine forensic urine samples from drug abusers. d-MA is the most common compound found in urine and mainly used by abusers.

Fabrication and application of cell-based microfluidic chip for eye-irritation test of chemicals (화학 물질의 안자극 시험용 세포 기반 미세유체 칩의 제작 및 응용)

  • Cho, Sujin;Rhee, Seog Woo
    • Analytical Science and Technology
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    • v.34 no.6
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    • pp.275-283
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    • 2021
  • This study presents the development of cell-based microfluidic chips for the performance of acute eye irritation tests due to chemicals and examined some of their applications. Microfluidic chips were fabricated by photolithography and soft lithography, and they had three compartments with different areas for cell culture. Rabbit corneal epithelial cells were used for the eye irritation test. The death of cells cultured inside the chip was monitored at regular time intervals after treatment with an aqueous solution of chemicals, and the cell death rate constants were calculated based on the viability curve. The performance of the microfluidic chip was verified by examining the effects of cell-cell junctions, cell-substrate adhesion, and initial cell numbers compared to cell death rates. Eye irritation tests were performed at various concentrations of an aqueous solution of sodium dodecyl sulfate (SDS), a standard substance for the eye irritant test. The cells were exposed to the SDS aqueous solution for 300 s, and the resulting eye irritation was assessed by cell viability. Finally, the equation for calculating the toxicity score (TS) was derived based on the weighting factor for each compartment in the chip. The cell-based microfluidic chip developed in this study may be used for eye irritation tests from chemicals used in cosmetics and pharmaceuticals.

Development of Work-related Musculoskeletal Disorder Questionnaire Using Receiver Operating Characteristic Analysis (Receiver Operating Characteristic 분석법을 이용한 업무관련성 근골격계질환 설문지 개발)

  • Kwon, Ho-Jang;Ju, Yeong-Su;Cho, Soo-Hun;Kang, Dae-Hee;Sung, Joo-Hon;Choi, Seong-Woo;Choi, Jae-Wook;Kim, Jae-Young;Kim, Don-Gyu;Kim, Jai-Yong
    • Journal of Preventive Medicine and Public Health
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    • v.32 no.3
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    • pp.361-373
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    • 1999
  • Objectives: Receive Operating Characteristic(ROC) curve with the area under the ROC curve(AUC) is one of the most popular indicator to evaluate the criterion validity of the measurement tool. This study was conducted to develop a standardized questionnaire to discriminate workers at high-risk of work-related musculoskeletal disorders using ROC analysis. Methods: The diagnostic results determined by rehabilitation medicine specialists in 370 persons(89 shipyard CAD workers, 113 telephone directory assistant operators, 79 women with occupation, and 89 housewives) were compared with participant's own replies to 'the questionnair on the worker's subjective physical symptoms'(Kwon, 1996). The AUC's from four models with different methods in item selection and weighting were compared with each other. These 4 models were applied to 225 persons, working in an assembly line of motor vehicle, for the purpose of AUC reliability test. Results: In a weighted model with 11 items, the AUC was 0.8155 in the primary study population, and 0.8026 in the secondary study population(p=0.3780). It was superior in the aspects of discriminability, reliability and convenience. A new questionnaire of musculoskeletal disorder could be constructed by this model. Conclusion: A more valid questionnaire with a small number of items and the quantitative weight scores useful for the relative comparisons are the main results of this study. While the absolute reference value applicable to the wide range of populations was not estimated, the basic intent of this study, developing a surveillance fool through quantitative validation of the measures, would serve for the systematic disease prevention activities.

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Determination of methamphetamine, 4-hydroxymethamphetamine, amphetamine and 4-hydroxyamphetamine in urine using dilute-and-shoot liquid chromatography-tandem mass spectrometry (시료 희석 주입 LC-MS/MS를 이용한 소변 중 메스암페타민, 4-하이드록시메스암페타민, 암페타민 및 4-하이드록시암페타민 동시 분석)

  • Heo, Bo-Reum;Kwon, NamHee;Kim, Jin Young
    • Analytical Science and Technology
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    • v.31 no.4
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    • pp.161-170
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    • 2018
  • The epidemic of disorders associated with synthetic stimulants, such as methamphetamine (MA) and amphetamine (AP), is a health, social, legal, and financial problem. Owing to the high potential of their abuse and addiction, reliable analytical methods are required to detect and identify MA, AP, and their metabolites in biological samples. Thus, a dilute-and-shoot liquid chromatography-tandem mass spectrophotometry (LC-MS/MS) was developed for simultaneous determination of MA, 4-hydroxymethamphetamine (4HMA), AP, and 4-hydroxyamphetamine (4HA) in urine. Urine sample ($100{\mu}L$) was mixed with $50{\mu}L$ of mobile phase consisting of 0.4 % formic acid and methanol and $50{\mu}L$ of working internal-standard solution. Aliquots of $8{\mu}L$ diluted urine was injected into the LC-MS/MS system. For all analytes, chromatographic separation was performed using a C18 reversed-phase column with gradient elution and a total run time of 5 min. The identification and quantification were performed by multiple reaction monitoring (MRM). Linear least-squares regression was conducted to generate a calibration curve, with $1/x^2$ as the weighting factor. The linear ranges were 2.0-200, 1.0-800, and 10-2500 ng/mL for 4HA and 4HMA, AP, and MA, respectively. The inter- and intraday precisions were within 6.6 %, whereas the inter- and intraday accuracies ranged from -14.9 to 11.3 %. The low limits of quantification were 2.0 ng/mL (4HA and 4HMA), 1.0 ng/mL (AP), and 10 ng/mL (MA). The proposed method exhibited satisfactory selectivity, dilution integrity, matrix effect, and stability, which are required for validation. Moreover, the purification efficiency of high-speed centrifugation was clearly higher than 6-15 % for QC samples (n=5), which was higher than that of the membrane-filtration method. The applicability of the proposed method was tested by forensic analysis of urine samples from drug abusers.

Estimation of Groundwater Recharge by Considering Runoff Process and Groundwater Level Variation in Watershed (유역 유출과정과 지하수위 변동을 고려한 분포형 지하수 함양량 산정방안)

  • Chung, Il-Moon;Kim, Nam-Won;Lee, Jeong-Woo
    • Journal of Soil and Groundwater Environment
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    • v.12 no.5
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    • pp.19-32
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    • 2007
  • In Korea, there have been various methods of estimating groundwater recharge which generally can be subdivided into three types: baseflow separation method by means of groundwater recession curve, water budget analysis based on lumped conceptual model in watershed, and water table fluctuation method (WTF) by using the data from groundwater monitoring wells. However, groundwater recharge rate shows the spatial-temporal variability due to climatic condition, land use and hydrogeological heterogeneity, so these methods have various limits to deal with these characteristics. To overcome these limitations, we present a new method of estimating recharge based on water balance components from the SWAT-MODFLOW which is an integrated surface-ground water model. Groundwater levels in the interest area close to the stream have dynamics similar to stream flow, whereas levels further upslope respond to precipitation with a delay. As these behaviours are related to the physical process of recharge, it is needed to account for the time delay in aquifer recharge once the water exits the soil profile to represent these features. In SWAT, a single linear reservoir storage module with an exponential decay weighting function is used to compute the recharge from soil to aquifer on a given day. However, this module has some limitations expressing recharge variation when the delay time is too long and transient recharge trend does not match to the groundwater table time series, the multi-reservoir storage routing module which represents more realistic time delay through vadose zone is newly suggested in this study. In this module, the parameter related to the delay time should be optimized by checking the correlation between simulated recharge and observed groundwater levels. The final step of this procedure is to compare simulated groundwater table with observed one as well as to compare simulated watershed runoff with observed one. This method is applied to Mihocheon watershed in Korea for the purpose of testing the procedure of proper estimation of spatio-temporal groundwater recharge distribution. As the newly suggested method of estimating recharge has the advantages of effectiveness of watershed model as well as the accuracy of WTF method, the estimated daily recharge rate would be an advanced quantity reflecting the heterogeneity of hydrogeology, climatic condition, land use as well as physical behaviour of water in soil layers and aquifers.