열분해/GC/MS에 의한 재현 단청 시편에서 아교의 확인

박종서,김미정,김순관 한국문화재보존과학회 2016 보존과학회지 Vol.32 No.1

아교는 나전, 목가구, 단청 등 문화재에 접착제 및 교착제로 광범위하게 사용돼 온 전통재료이다. 아교의 분석과 확인은 주로 IR에 의한 작용기의 확인을 통해 이루어졌으나 몇 가지 물질이 섞여 있는 경우 밴드의 중복 등에 의해 명확하게 아교를 확인하는데 어려움이 있다. 열분해/GC/MS분석은 소량의 시료로 열분해 산물의 화학성분을 알 수 있어 아교 등 고분자 재료의 성분을 분석하는데 유용하다. 본 연구에서는 단청 시편에서 아교를 이 방법으로 확인하고자 하였다. 우선, 단청 채색에 사용되는 아교, 동유에 대한 열분해/GC/MS 분석을 실시하여 주요하면서 특징적인 열분해산물을 확인하였다. 또한, 뇌록을 칠한 단청시편을 제작하여 열충격 시험과 인공 풍화 시험 후에 분석을 했을 때 약화가 되긴 하였지만 아교의 특징적인 peak의 검출이 가능하였다. 이로부터, 단청과 같이 다양한 재료와 풍화상태로 구성된 문화재에서 아교의 검출이 열분해/GC/MS로 가능함을 확인하였다. 아울러, 단청 시편을 IR로 분석하여 IR과 열분해/GC/MS 분석 간에 아교 검출 능력을 비교하였다. Animal glue is a traditional material used extensively as adhesive and binder in mother-of-pearl, wooden structure, traditional painting, etc. Analysis of animal glue is usually performed with IR(infrared spectroscopy) based on the IR absorption of functional group. But, it has a limitation in confirming animal glue when a sample consists of several materials because of overlapping of the absorption band. Py/GC/MS(pyrolysis/gas chromatography/mass spectrometry) is a useful tool in analyzing the constituent of polymeric materials like animal glue by identifying their pyrolysate with very small amount of sample. In this study, confirmation of animal glue in a Dancheong sample was tried with this method. Characteristic pyrolytic compounds of animal glue and tung oil used in Dancheong were identified. Dancheong sample painted with Noerok as a coloring material, animal glue and tung oil was prepared and it was possible to find characteristic peaks of animal glue after thermal degradation and artificial weathering experiment. From this, we found that animal glue can be detected using py/GC/MS in cultural heritage samples consisting of several materials and in different condition. IR was also tried to analyze Dancheong sample and the results were compared with those of py/GC/MS for the detection of animal glue.

06 식품의약품안전처 SESSION : GC-MS/MS를 이용한 국내 미등록 농약의 현미 중 다성분 동시 분석

이종화,차경훈,신용호,성정희,김병준,김은혜,김정한 한국환경농학회 2014 한국환경농학회 학술대회집 Vol.2014 No.-

GC-MS/MS 분석대상 농약의 선정을 위하여 국내 미등록 농약 79성분을 대상으로 개별 표준용액을 조제한 후 GC-MS full scan 분석을 통하여 GC 분석이 가능한 지를 검토하였고, 이 중 10 성분(2,6-Diisopropylnaphthalene, Butylate, Chlorflurenol-methyl, Dichlomid, EPTC, Flumetralin, Flutriafol,Prometon, Prosulfocarb, Quinoxyfen)만이 GC-MS/MS 분석이 가능함을 확인하였다. GC-MS/MS 기기분석조건의 확립을 위하여, 성분당 2개의 적정 precursor ion을 선정하였고, product ion scan 분석을 통해 한 성분 당 2개의 SRM (Selected reaction monitoring) 이온을 선정하여 분석의 신뢰성을 높였다. 정량을 위한 검량선은 0.002 mg kg-1에서 0.2 mg kg-1까지 matrix matched calibration법을 사용하였으며, EPTC와 Flumetralin 제외한 모든 성분에서 검량선 상관 계수(R2)는 0.99 이상이었고, 정량한계는 0.001-0.050 mg kg-1 범위였다. 시료의 전처리를 위하여 분쇄한 현미 5 g을 0.1% formic acid가 함유된 acetonitile로 추출 하였고 4 g MgSO4, 1 g NaCl, 1 g NaCitrate, 0.5 gdisodium citrate sesquihydrate를 가하여 진탕한 후, 원심분리한 상등액을 dispersive SPE (50 mgPSA, 150 mg MgSO4)를 이용하여 정제하여 기기분석을 위한 시료로 사용하였다. 이상의 전처리법을 이용하여 현미에 대하여 0.01 및 0.05 mg kg-1농도에서 회수율을 측정한 결과, 93.1∼124.4 %(0.01 mg kg-1 처리수준), 92.4∼115.4 %(0.05 mg kg-1 처리수준)의 양호한 회수율을 보였다. Flutriafol과 Prometon은 기기분석에서의 감도가 낮았으며, EPTC와 Flumetralin는 시료에서의 간섭물질로 인하여 검량선 및 회수율 측정이 불가능하여 이상 4가지 성분은 GC-MS/MS를 이용한 분석이 용이하지 않아 LC-MS/MS를 이용한 분석을 검토할 필요가 있음 확인하였다.

PAHs 농도 분포에 따른 GC/MS와 HPLC의 분석특성에 관한 연구

홍좌령 ( Jwa Ryung Hong ),최광민 ( Kwang Min Choi ) 한국산업보건학회 2015 한국산업보건학회지 Vol.25 No.3

Objectives: The purpose of this study was to determine the best method to analyze PAHs at extremely low concentrations. To this end, 16 PAHswere analyzed simultaneously by GC/MS, HPLC/FLD and HPLC/UVD, and the analytical characteristics of HPLC and GC/MS were compared. Methods: This study was conducted by GC/MS and HPLC/FLD/UVD, and evaluated linearity, precision and detection limit. Standard solutions were prepared for 21 samples in the range of 0.00001~1.0 ㎍/mL and the samples were divided into four groups. All samples were made in three sets and analysis was replicated seven times. Results: Sixteen PAHs could be simultaneously separated by HPLC and GC/MS, and the adequate equipment was HPLC/FLD. The retention times by HPLC were shorter than GC/MS, and HPLC had better separation for most PAHs than GC/MS. The peaks of naphthalene and naphthalene-D8 partially overlapped for GC/MS. HPLC/FLD had a 20-2000 times lower limit of detection than GC/MS and UVD. However FLD was not adequate for analyzing acenaphthylene because it has too low a fluorescence quantum yield to be detected. The precision of HPLC/FLD/UVD and GC/MS showed less than 20% at 0.001 ㎍/mL PAHs and when the concentration was higher, the coefficient of variation was decreased. HPLC/FLD was better for the overall detection of limits. Conclusions: The results indicate that the HPLC/FLD method has good linear range, precision and a detection of limits from 0.00001~0.0001 ㎍/mL for all 16 PAHs. This study contributes to providing useful data for analysis technology and can be applied to occupational exposure measurement for PAHs in workplaces.

GC-MS/MS를 이용한 한강수계 및 상수도계통에서 N-nitrosamines 조사

윤우현 ( Woo-hyun Yoon ),이준호 ( Jun-ho Lee ),이현주 ( Hyun-ju Lee ),이수원 ( Su-won Lee ),안재찬 ( Jae-chan Ahn ),김복순 ( Bog-soon Kim ) 한국물환경학회 2016 한국물환경학회지 Vol.32 No.5

This study was conducted to improve the analysis method used for N-nitrosamines and to investigate the occurrences of N-nitrosamines in tributaries of the Han-river, intake stations, water treatment plants and tap water used within the city of Seoul. The samples were pretreated through a solid phase extraction and analyzed using a gas chromatography tandem mass spectrometer (GC-MS/MS). The GC-MS/MS in CI mode was compared with the GC-MS/MS in EI mode by the method detection limits (MDLs). MDLs by GC-CI/MS/MS and GC-EI/MS/MS were 0.2 ~ 1.1 ng/L and 0.2 ~ 1.4 ng/L, respectively. Samples were collected from ten tributaries of the Han-river (T1 ~ T10), six intake stations (II ~ 16), six water treatment plants (P1 ~ P6) and 25 taps in Seoul city. The maximum levels of N-nitrosodimethylamine (NDMA) were 0.013 ㎍/L, 0.008 ㎍/L, 0.006 ㎍/L and 0.002 ㎍/L in tributary water, raw water, finished water and tap water samples, respectively. Detected levels were much lower than 0.1 ㎍/L corresponding to the guideline value of WHO.

LC-MS/MS와 GC-MS/MS를 이용한 사과와 쌀 시료에서 320종 농약의 다성분 분석

김종환(Jong-Hwan Kim),김영진(Yeong-Jin Kim),권영상(Young-Sang Kwon),서종수(Jong-Su Seo) 한국농약과학회 2016 농약과학회지 Vol.20 No.2

A new analytical method has been developed to determine 320 pesticides in apple and rice. The extraction of pesticides was carried out based on QuEChERS sample extraction, and determination was performed using LC-MS/MS and GC-MS/MS. 320 pesticides were selected for experiments. 251 and 110 pesticides among them were analysed by LC-MS/MS and GC-MS/MS, respectively. 41 pesticides of them were analyzed by both GC-MS/MS and LC-MS/MS. Among pesticides analysed by LC, 242 pesticides (96% of total number) in apple and 237 pesticides (94% of total number) in rice showed recoveries in the range of 70~120% with RSD ≤ 20%. In case of pesticides analyzed by GC-MS/MS, 103 pesticides (94% of total number) in apple and 83 pesticides (76% of total number) in rice were successfully validated. These results indicated that LC-MS/MS and GC-MS/MS analysis with the QuEChERS sample preparation can be partly applied to multi-residue pesticides in agricultural products.

GC-MS/MS를 이용한 원유 원료 중 농약 동시분석법 확립

최영내,신윤호,조황의,김정복,Young Nae Choi,Yoon ho Shin,Hwangeui Cho,Jung Bok Kim 한국식품위생안전성학회 2023 한국식품위생안전성학회지 Vol.38 No.6

본 연구에 선정된 농약성분은 사용목적에 따른 분류 기준으로 살충제에 해당되며, 유효성분 조성에 따른 분류의 경우 유기인계 농약성분 2가지, 농약 중 가장 범용적으로 사용되고 있는 피레스로이드 농약성분 3가지이다. 원유 중 5가지 농약성분인 chlorpyrifos, chlorpyrifos-methyl, cypermethrin, deltamethrin 및 permethrin 등은 시료와 분석물질의 특성을 고려하여 2그룹으로 나누어 시료전처리를 확립하였고 LLE와 카트리지를 이용하여 원유 중에 농약성분을 분석하였다. GC-MS/MS을 이용하였고 사용된 컬럼은 HP-5MS(30 m×0.25 mm ID, 0.25 ㎛)를 사용하였다. 검량선의 농도는 10-200 ng/mL이고, 각각의 분석물질의 결정계수(R²)가 0.997 이상으로 확인하였다. 정밀성과 정확성을 확인하기 위해 검량선 내 3가지 농도 선정하여 일내와 일간의 정밀성 및 정확성을 측정하였다. 5개의 분석물질의 일내 일간 정밀성은 10.3% 이하, 정확성은 100.9-117.5%의 범위로 확인되었다. 확립된 분석법의 회수율 측정을 위해 농약기준 규격의 잔류허용기준을 참고하여 가장 낮은 농도를 선정하였고 회수율은 86.1%-102.1%로 확인되었다. 물질의 검출한계 및 정량한계의 농도 범위는 37.5-125 ng/mL로 산출되었다. 측정 불확도를 산출하기 위해 설정된 불확도 요인을 설정하여 산출하였다. 그 결과 신뢰수준 95% k=2에서 chlorpyrifos 6.35±0.32 mg/kg, chlorpyrifos-methyl 6.20±0.17 mg/kg, cypermethrin 6.45±0.45 mg/kg, deltamethrin 6.28±0.20 mg/kg, permethrin 6.10±0.56 mg/kg 으로 불확도 값을 산출하여 원유 중 5가지 농약 성분의 유효성이 검증된 분석법을 확립하였다. 본 연구결과를 통해 원유 중 미량으로 잔류할 수 있는 농약성분의 검출이 가능한 것으로 나타났다. 본 연구결과는 기준규격 설정과 관리에 좋은 참고 자료가 될 것으로 판단된다. GC-MS/MS using liquid-liquid extraction (LLE) and C18 cartridges was used to identify and quantify levels of chlorpyrifos, chlorpyrifos-methyl, cypermethrin, deltamethrin and permethrin in bulk raw milk. A calibration curve spanning 10 ng/mL to 200 ng/mL was obtained with a satisfactory correlation coefficient of 0.99. The limits of detection (LOD) and limits of quantitation (LOQ) for chlorpyrifos, chlorpyrifos-methyl, cypermethrin, deltamethrin, and permethrin in the matrix ranged from 0.06 to 1.81 ng/mL and 0.19 to 6.04 ng/mL, respectively. The recoveries of 5 pesticides from spiked samples at 37.5-125 ng/mL ranged from 86.1 to 102.1%. The measurement of uncertainty of the GC-MS/MS method for these five pesticides was developed based on the analytical process and quantification. An analysis method that is easier and faster than the method specified in the Korean food standards codes for analyzing these five pesticides in raw material milk was developed. Moreover, the analytical method for chlorpyrifos, chlorpyrifos-methyl, cypermethrin, deltamethrin, and permethrin in bulk raw milk by GC-MS/MS was established.

LC-MS/MS 및 GC-MS/MS를 활용한 수산물 중 디아제팜의 정량분석법 개발

신다솜,강희승,김주혜,정지윤,이규식,Shin, Dasom,Kang, Hui-Seung,Kim, Joohye,Jeong, Jiyoon,Rhee, Gyu-Seek 한국식품위생안전성학회 2018 한국식품위생안전성학회지 Vol.33 No.2

본 연구는 국내 생산 및 수입 양식 수산물에 대해 잔류할 수 있는 향정신성 의약품인 디아제팜 대한 안전관리강화기반을 위해 마련되었다. 중국인민공화국 국가 표준시험법(GB 29697-2013)을 기반으로 전처리 방법을 개선하여 GC-MS/MS 시험법을 확립하였으며, LC-MS/MS 방법과의 기기간 검증을 통해 확립된 시험법의 선택성, 정량한계 및 회수율에 대한 검증을 통해 디아제팜 시험법으로서의 유효성을 확인하였다. LC-MS/MS의 경우 아세토니트릴로 추출 후 PSA를 이용해 정제하였고, GC-MS/MS의 경우 아세토니트릴로 추출후 $C_{18}$카트리지를 이용해 정제하였다. 디아제팜은 표준용액을 정량한계를 포함한 농도에 따라 검량선을 작성한 결과 두 기기 모두 $r^2$> 0.99 이상의 직선성을 확인하였다. 본 실험에서의 검출한계와 정량한계는 LC-MS/MS 및 GC-MS/MS 모두 0.0004 mg/kg, 0.001 mg/kg 수준이었으며, 평균 회수율은 각각 99.8~106%, 109~124%이었다. 또한, 분석오차는 모두 15% 이하로 정확성 및 재현성이 우수하였으며, CODEX 가이드라인 규정에 만족하는 수준이었다. 따라서 개발된 시험법은 안전한 수산물의 국내 유통과 잔류실태조사를 위해 활용될 것으로 기대한다. The aim of this study was to develop an analytical method for the quantification of diazepam residues in fishery products, using liquid and gas chromatography-tandem mass spectrometry (LC-MS/MS and GC-MS/MS). The sample utilized in the study was extracted from the fish sample (crucian carp) using 0.1% formic acid in acetonitrile. For the utilization of the purification process, the dispersive solid phase extraction (dSPE) was used for LC-MS/MS, dSPE and SPE was used for GC-MS/MS, respectively. To be sure, the standard calibration curves showed a good linearity as the noted correlation coefficients, $r^2$ was > 0.99. The average recoveries for accuracy ranged in 99.8~124% for the samples which were fortified at three different levels (0.001, 0.002 and 0.010 mg/kg). The correlation coefficient for the precision effect was measured at a range of 4.01~11.8%. The limit of detection (LOD) for the diazepam analysis was 0.0004 mg/kg, and the limit of the quantification (LOQ) was 0.001 mg/kg. The proposed analytical method was characterized with a high accuracy and acceptable sensitivity to meet the established Codex Alimentarius Commission (CAC/GL71-2009) guideline requirements. We therefore established the optimal analysis method for the determination of diazepam in the fishery products using LC-MS/MS and GC-MS/MS. It would be applicable to analyze the diazepam residues in fishery products in further studies on this subject.

Multi-dimensional GC-MS를 이용한 항공터빈유의 첨가제 분석

연주민,장윤미,임의순,김성룡,강용 한국응용과학기술학회 2018 한국응용과학기술학회지 Vol.35 No.4

To improve fuel performance and specific characteristics of long storage and moving through fuel systems additives should be added in kerosene type aviation turbine fuel (AVTUR) such as antioxidant, fuel system icing inhibitor (FSII), electric conductivity improvers and so on. The dosage of additives has to be analyzed qualitatively and quantitatively due to inspect the quality of abnormal fuel and distinguish other petroleum products. Multi-dimensional GC-MS (MDGC-MS) with Deans switching technique are applied the determination of antioxidant and FSII, which are added with AVTUR containing complex mixture of hydrocarbons. Antioxidant and FSII in the range of 2.5–20 mg/L was quantitatively and qualitatively analyzed using MDGC-MS and the detection limit was about twice as low as that of the 1-dimensional GC-MS results. The method in this study has been higher peak resolution compared with GC-MS and could be simultaneously analyzed different two additives without sample pre-treatment. 항공터빈유는 등유 기반의 석유제품에 산화 방지제(Antioxidant), 빙결 방지제(Fuel system icing inhibitor, FSII), 전기전도도 향상제(Electrical conductivity improver) 등의 첨가제를 첨가하여 항공기 연료로서 필요한 성능 향상 및 보관이나 이송 등에 관한 특정한 능력을 부여시키고 있다. 이들 첨가제는 항공 터빈유의 품질에 이상이 발생하거나 다른 석유제품과 구별하기 위하여 그 첨가량을 정성 및 정량적으로 분석할 수 있어야 한다. 항공터빈유는 수많은 탄화수소 화합물로 구성된 복잡한 화합물이기 때문에 미량으로 첨가된 산화 방지제와 빙결 방지제를 분석하기 위하여 Multi-dimensional GC-MS (MDGC-MS)의 Deans switching 기술을 적용하였다. 2.5 - 20 mg/L 농도 범위의 산화 방지제와 빙결 방지제를 MDGC-MS로 정량 및 정성적으로 분석할 수 있었으며, 검출 한계는 1-dimensional GC-MS의 분석 결과와 비교하여 약 2배 정도 낮았다. 본 연구에서 개발된 시험 방법은 기존의 GC-MS보다 첨가제 피크의 분리능이 더 우수하였으며, 시료의 전처리가 필요없이 두 가지 첨가제를 동시에 분석할 수 있었다.

Comparative GC-MS Based In vitro Assays of 5α-Reductase Activity Using Rat Liver S9 Fraction

Su Hyeon Lee,Dong-Hyoung Lee,Jeongae Lee,Won-YongLee,Bong Chul CHUNG,Man Hoi 사단법인 한국질량분석학회 2012 Mass spectrometry letters Vol.3 No.1

5α-Dihydrotestosterone (DHT) is the primary active metabolite of testosterone, catalyzed by 5α-reductase (5αR) in the skin, prostate, and liver. In this study, the 5αR activity in rat liver S9 fraction in the presence of a NADPH-generating system was evaluated and compared by gas chromatography-mass spectrometry (GC-MS)-based in vitro assays. Testosterone and a 5αR inhibitor, finasteride, were added to the S9 fractions and incubated at 37oC for 1 h. Both testosterone and DHT were quantitatively measured and compared with two different GC-MS-based steroid profiling techniques. DHT was not detected by conventional GC-MS analysis in the absence of finasteride when the concentration of testosterone in the S9 fraction was less than 0.2 μM, whereas the isotope-dilution GC-MS (GC-IDMS) system was able to evaluate the 5αR activity. Because the S9 fraction contains more reactive enzymes and is easier to collect from tissues compared with a microsomal solution, the combination of the S9 fraction and GC-IDMS technique may be a promising assay for evaluating the 5αR activity in large-scale clinical studies. 5α-Dihydrotestosterone (DHT) is the primary active metabolite of testosterone, catalyzed by 5α-reductase (5αR) inthe skin, prostate, and liver. In this study, the 5αR activity in rat liver S9 fraction in the presence of a NADPH-generating systemwas evaluated and compared by gas chromatography-mass spectrometry (GC-MS)-based in vitro assays. Testosterone and a5αR inhibitor, finasteride, were added to the S9 fractions and incubated at 37oC for 1 h. Both testosterone and DHT were quantitativelymeasured and compared with two different GC-MS-based steroid profiling techniques. DHT was not detected by conventionalGC-MS analysis in the absence of finasteride when the concentration of testosterone in the S9 fraction was less than0.2 μM, whereas the isotope-dilution GC-MS (GC-IDMS) system was able to evaluate the 5αR activity. Because the S9 fractioncontains more reactive enzymes and is easier to collect from tissues compared with a microsomal solution, the combination ofthe S9 fraction and GC-IDMS technique may be a promising assay for evaluating the 5αR activity in large-scale clinical studies.

교반막대 추출법과 GC-MS/MS를 이용한 수중의 합성 향물질류 분석

서창동(Chang Dong Seo),손희종(Hee Jong Son),염훈식(Hoon Sik Yoom),최진택(Jin Taek Choi),류동춘(Dong Choon Ryu),권기원(Ki Won Kwon),장성호(Seung Ho Jang) 大韓環境工學會 2014 대한환경공학회지 Vol.36 No.6

본 연구에서는 SBSE 전처리 장치와 GC-MS/MS를 이용하여 합성 향물질 11종을 동시 분석할 수 있는 분석법을 개발하기 위해 흡착 bar의 교반시간, 교반속도, 시료수의 pH, 시료수 용량, 염석제 투입량 및 메탄올 주입량 변화 등 SBSE (stir barsorptive extraction) 전처리 조건과 GC-MS/MS (gas chromatography/tandem mass spectrometry)의 기기조건을 다양하게 변화시켜 SBSE-GC-MS/MS를 이용한 분석법을 개발하였다. 11종의 합성 향물질들에 대한 검출한계(LOD)는 2.1~4.1 ng/L였으며, 정량한계(LOQ)는 6.6~12.9 ng/L였다. 수돗물, 낙동강 원수, 하수처리장 최종방류수 및 해수를 이용하여 시료수의 matrix 영향을살펴본 결과, 11종의 합성 향물질들의 회수율 및 RSD의 경우 각각 88%~119% 및 0.8%~7.5%로 양호한 결과를 나타내어 시료수의 matrix 영향을 받지 않는 것으로 나타났다. 본 연구에서 개발된 SBSE-GC-MS/MS 분석법은 40 mL 정도의 적은 시료수량으로도 고감도 분석이 가능하며, 용매류를 사용하지 않기 때문에 분석자의 건강 및 환경친화적인 분석법이라는 장점뿐만 아니라 간편하고, 빠르며 자동화된 방법이라는 장점을 가진다. A highly sensitive analytical method based on stir bar sorptive extraction (SBSE) technique and gas chromatography/tandem mass spectrometry (GC-MS/MS) has been developed, allowing the simultaneous multi-analyte determination of 11 syntheticfragrances (SFs) in water samples. The stir bar coated with polydimethylsiloxane (PDMS) was added to 40 mL of water sample atpH 3 and stirred at 1,100 rpm for 120 min. Other SBSE parameters (salt effect and presence of organic solvent) were optimised. The method shows good linearity (coefficients > 0.990) and reproducibility (RSD < 10.9%). The extraction efficiencies were above83% for all the compounds. The limits of detections (LOD) and limits of quantification (LOQ) were 2.1~4.1 ng/L and 6.6~12.9ng/L, respectively. The developed method offers the ability to detect 11 SFs at ultra-low concentration levels with only 40 mL ofsample volume. Matrix effects in tap water, river water, wastewater treatment plant (WWTP) final effluent water and seawaterwere investigated and it was shown that the method is suitable for the analysis of trace level of 11 SFs. The method developedin the present study has the advantage of being rapid, simple, high-sensitive and both user and environmentally friendly.