• 농약과학회지
• /
• 제19권3호
• /
• pp.185-194
• /
• 2015

본 연구는 대부분의 농작물 중 살균제 carpropamid의 잔류량을 정밀하게 분석할 수 있는 단성분 분석법을 개발하고자 하였다. 대표 농작물로 배추, 사과, 현미, 고추를 선정하였으며, 균질화된 농작물 시료 중 carpropamid 잔류분을 acetone을 이용하여 진탕 추출하고 액-액 분배법과 Florisil 크로마토그래피법을 통해 정제하였다. C8 및 C18 역상컬럼이 장착된 액체크로마토그래피를 이용해 UV 220 nm 파장에서 carpropamid를 정량분석하였으며, 질량분석기를 통해 잔류분을 확인하였다. 본 분석법을 통한 carpropamid의 기기정량한계는 2 ng으로 분석정량한계는 0.02 mg/kg이었다. 표준용액을 3수준 (분석정량한계 ${\times}1$, ${\times}10$, ${\times}100$), 3반복으로 무처리 시료에 첨가하고 본 분석법의 회수율을 산출한 결과 84~112%이었으며, 농산물 종류에 상관없이 반복 간 분석오차는 10% 미만으로 우수한 정밀성을 보였다.

• 한국환경농학회지
• /
• 제34권2호
• /
• pp.111-119
• /
• 2015

BACKGROUND: Ethychlozate (ECZ) is a plant growth regulator of synthetic auxin for agricultural commodities (ACs). Accurate and sensitive method to determine ECZ in diverse ACs on global official purpose is required to legal residue regulation. As the current official method is confined to the limited type of crops with poor validation, this study was conducted to improve and extend the ECZ method using high-performance liquid chromatography (HPLC) in all the registered crops with method verification. METHODS AND RESULTS: ECZ and its acidic metabolite (ECZA) were both extracted from acidified samples with acetone and briefly purified by dichloromethane partition. ECZ was hydrolyzed to form ECZA and the combined ECZA was finally purified by ion-associated partition including hexane-washing. The instrumental quantitation was performed using HPLC/ FLD under ion-suppression of ECZA with no interference by sample co-extractives. The average recoveries of intra- and inter-day experiment ranged from 82.0 to 105.2% and 81.7 to 102.8%, respectively. The repeatability and reproducibility for intra- and inter-day measurements expressed as a relative standard deviation was less than 8.7% and 7.4%, respectively. CONCLUSION: Established analytical method for ECZ residue in ACs was applicable to the nation-wide pesticide residues monitoring program with the acceptable level of sensitivity, repeatability and reproducibility.

• Bulletin of the Korean Chemical Society
• /
• 제27권6호
• /
• pp.903-908
• /
• 2006

Various extraction procedures were investigated using reference materials and samples to evaluate extraction efficiency and effectiveness. Inductively coupled plasma mass spectrometry (ICP-MS) was used to measure total arsenic and to quantitate arsenic species when coupled to an HPLC (high pressure liquid chromatography). Arsenic species were extracted from rice flour (NIST SRM 1568a) with water/methanol mixtures using accelerated solvent extraction (ASE). Total arsenic extraction efficiency ranged from 42 to 64%, for water and various methanol concentrations. From spinach (NIST SRM 1570), freeze-dried apple, and rice flour (NIST SRM 1568a), arsenic species were extracted with trifluoroacetic acid (TFA) at 100 ${^{\circ}C}$. Total arsenic extraction efficiency was 90% for spinach, 75% for freeze-dried apple, and 83% for rice flour. Enzymatic extraction with alpha-amylase and sonication resulted in extraction efficiency of 104% for rice flour, 98% for freeze-dried apple, and 7% for spinach. Chromatograms of arsenic species extracted by the optimum extraction methods were obtained, and the species were quantified. Arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) were found in the apple sample, and DMA and As(V) in the rice flour sample. As(V) and MMA were found in three herbal dietary supplement samples.

• Bulletin of the Korean Chemical Society
• /
• 제32권5호
• /
• pp.1547-1553
• /
• 2011

An effective analytical method of gas chromatography/mass spectrometry (GC/MS) was developed for the rapid determination of essential oils in the crude extract of Acorus species (Acorus gramineus, Acorus tatarinowii, and Acorus calamus). Major phenypropanoids (${\beta}$,${\alpha}$-asarone isomers, euasarone, and methyleugenol) and ${\beta}$-caryophyllene in Acorus species were used as marker compounds and determined for the quality control of herbal medicines. To extract marker compounds, various extraction techniques such as solvent immersion, mechanical shaking, and sonication were compared, and the greatest efficiency was observed with sonication extraction using petroleum ether. The dynamic range of the GC/MS method depended on the specific analyte; acceptable quantification was obtained between 10 and 2000 ${\mu}g/mL$ for ${\beta}$-asarone, 10 and 500 ${\mu}g/mL$ for ${\alpha}$-asarone, 10 and 200 ${\mu}g/mL$ for methyleugenol, and between 5 and 100 ${\mu}g/mL$ for ${\beta}$-caryophyllene. The method was deemed satisfactory by inter- and intra-day validation and exhibited both high accuracy and precision, with a relative standard deviation < 10%. Overall limits of detection were approximately 0.34-0.83 ${\mu}g/mL$, with a standard deviation (${\sigma}$)-to-calibration slope (s) ratio (${\sigma}$/s) of 3. The limit of quantitation in our experiments was approximately 1.13-3.20 ${\mu}g/mL$ at a ${\sigma}$/s of 10. On the basement of method validation, 20 samples of Acorus species collected from markets in Korea were monitored for the quality control. In addition, principal component analysis (PCA) and hierarchical cluster analysis (HCA) were performed on the analytical data of 20 different Acorus species samples in order to classify samples that were collected from different regions.

• Bulletin of the Korean Chemical Society
• /
• 제35권5호
• /
• pp.1455-1459
• /
• 2014

We report a sensitive and reliable FRET-based nanotechnology assay for efficient detection and quantification of bisulfite-unmodified or modified DNA. Bisulfite-untreated DNA or bisulfite-treated DNA is subjected to PCR amplification with biotin-conjugated primers so that the amounts of bisulfite-untreated and treated DNA can be differentiated. Streptavidin-coated quantum dots (QDs) are used to capture biotinylated PCR products intercalated with SYBR Green, enabling FRET measurement. Key features of our method include its low intrinsic background noise, high resolution, and high sensitivity, enabling detection of as little as 1.75 ng of bisulfite-untreated DNA in the presence of an approximately 1,000-fold excess of bisulfite-untreated DNA compared to bisulfate-treated DNA, with the use of PCR reduced (as low as 15 cycles). SYBR Green as an intercalating dye as well as a FRET acceptor allows for a single-step preparation without the need for primers or probes to be chemically conjugated to an organic fluorophore. Multiple acceptors per FRET donor significantly enhance the signal-to-noise ratio as well. In consideration of the high relevance of bisulfite treatment to DNA methylation quantitation, our system for FRET measurement between QDs and intercalating dyes can be generally utilized to analyze DNA methylation and to potentially benefit the scientific and clinical community.

• 대한화학회지
• /
• 제51권2호
• /
• pp.147-153
• /
• 2007

간단하고 선택적인 흐름주입촉매법으로 pH 1.0에서 고황산염(periodate)에 의한 pyronin B의 산화의 촉매 효과를 근간으로 루테늄 정량에 대해 논하였다. 반응속도는 555 nm에서의 흡수를 분광광도법으로 조절하였다. 루테늄 정량의 최적화된 조건으로 검출한계는 0.04 ng/mL로 측정범위로 0.1-10.0 ng/mL(r2=0.9982)와 10.0-50.0 ng/mL (r2=0.9934), 그리고 시료속도는 30±5 samples/h를 얻었다. 5번 측정의 상대표준편차는 1.44%를 넘지 않았다. 제안된 본 방법은 성공적으로 환경 및 생물학적 시료 중에서 루테늄의 초미량 정량에 성공적으로 적용되었다.

• 디지털융복합연구
• /
• 제10권6호
• /
• pp.331-339
• /
• 2012

The easy and simple simultaneous analytical method of preservatives (BA, SA, DHA, MP, EP, IPP, PP, IBP and BP) was studied by more easily changing from method used in food and drug using HPLC with scherzo SM-C18 column. All presevatives were seperated successfully in mobile phase of 50 mM ammonium formate : 0.1% phosphoric acid (50:50 v/v%) and 50 mM ammonium formate : acetonitrile (30 : 70). Retention time of BA, SA, DHA, MP, EP, IPP, PP, IBP and BP was 7.74, 9.08, 12.57, 13.83, 21.62, 27.29, 28.20, 33.20 and 33.68 min, respectively. The calibration curves of BA, SA, DHA, MP, EP, IPP, PP, IBP and BP were linear over the concentration range of 5~80 ${\mu}g/mL$ with correlation coefficient of above 0.999. The limit of detection (LOD) and limit of quantitation (LOQ) of BA, SA, DHA, MP, EP, IPP, PP, IBP and BP were 0.52 and 1.58, 1.09 and 3.29, 1.00 and 3.03, 1.36 and 4.13, 1.26 and 3.83, 1.02 and 3.08, 1.11 and 3.37, 0.82 and 2.48, 0.85 and 2.59 ${\mu}g/mL$, respectively. The coefficients of variation for intra- and inter-day assay were 0.12~2.68 and 0.18~2.66%, respectively. The developed method showed good intra- and inter-day precision and accuracy. The preservatives used in mouthwashes were BA, MP and PP and were detected in 24 samples(86%) except for 4 samples and not showed significant difference in using dose of adult and children. In conclusion, the developed method can be useful for simultaneous analysis of preservatives in mouthwashes and these results suggest that could be applied to fundamental study and guideline on content of preservatives in mouthwashes.

• 분석과학
• /
• 제33권3호
• /
• pp.125-133
• /
• 2020

Methylisothiazolinone (MIT) and chloromethylisothiazolinone (CMIT) cause allergic contact dermatitis and are banned cosmetics ingredients, except in rinse-off products. However, their presence has been detected in cosmetics. We report a UPLC-tandem MS/MS screening method for their simultaneous determination in cosmetics. To facilitate extraction from various matrices, pretreatment methods were developed for each sample type. The method was optimized through a series of assessments, including specificity, LOD, LOQ, linearity, recovery, stability, precision, and accuracy. The LODs and LOQs for MIT ranged from 0.054 and 0.163 ㎍ mL^-1 whereas those for CMIT ranged from 0.040 and 0.119 ㎍ mL^-1. The linear correlation coefficients (r²) were higher than 0.999. Relative standard deviations (RSDs) for both intra- and inter-day measurements ranged from 0.3 ~ 13.6 %. Recoveries at three different concentrations were within 87.9 ~ 118.9 %. The RSD for stability measurements of spiked samples was within 7 %. These results confirm the suitability of the developed method for the simultaneous quantitation of MIT and CMIT in cosmetics. Samples of 320 color cosmetics, including eyeshadows, solid lipsticks, liquid lipsticks, and nail polishes were analyzed using the developed method, and two of them were found to contain both MIT and CMIT and one of them was found to contain only MIT. This data and the method will aid the regulation of ingredients used in cosmetics.

• 한국환경농학회지
• /
• 제37권2호
• /
• pp.117-124
• /
• 2018

본 연구에서는 HPLC-UVD/MS를 이용하여 농산물 중 oxanthiin 살균제인 oxycarboxin의 잔류 분석법을 확립하였다. 대표 농산물은 현미, 콩, 배추, 고추 및 사과를 선정하였고 acetone을 가하여 추출된 oxycarboxin 성분을 dichloromethane 액-액 분배법과 Florisil 흡착크로마토그래피법으로 정제하여 HPLC-UVD/MS 분석대상 시료로 사용하였다. Oxycarboxin의 정량적 분석을 위한 최적 분석 조건을 확립하였으며, 정량한계(LOQ)는 0.04 mg/kg 이었다. 각 대표 농산물에 대해 정량한계, 정량한계의 10배 및 50배 수준에서 회수율을 검토한 결과 모든 처리농도에서 78.3~96.1% 수준을 나타내었으며, 반복 간 변이계수(CV)는 최대 4.7%를 나타내어 잔류분석 기준인 회수율 70~120% 및 분석오차 10% 이내를 충족시키는 만족한 결과를 도출하였으며, LC/MS SIM을 이용하여 실제 농산물 시료에 적용하여 재확인 하였다. 이상의 결과로 신규 oxycarboxin의 HPLC-UVD/MS 분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족하는 신뢰성이 확보된 정량 분석법으로 사용 가능할 것이다.

• 한국축산식품학회지
• /
• 제35권4호
• /
• pp.466-472
• /
• 2015

A rapid and simple analytical method, using liquid chromatography tandem mass spectrometry (LC-MS/MS), was developed to detect myo-inositol (MI) in infant formulas. For protein removal: acid hydrolysis and lipid removal through organic solvent extraction. The operating conditions for instrumental analysis were determined based on previously reported analogous methods that used LC-MS/MS. Quantitative analysis was used for the detection limit test, infant formula recovery test, and standard reference material (SRM) 1849a to verify the validity of our LC-MS/MS analytical method, which was developed to quantify MI. For validation, the results of our method were compared with the results of quantitative analyses of certified values. The test results showed that the limit of detection was 0.05 mg/L, the limit of quantitation was 0.17 mg/L, and the method detection limit was 17 mg/kg. The recovery test exhibited a recovery between 98.07-98.43% and a relative standard deviation between 1.93-2.74%. Therefore, the result values were good. Additionally, SRM 1849a was measured to have an MI content of 401.84 mg/kg and recovery of 98.25%, which is comparable to the median certified value of 409 mg/kg. From the aforementioned results, we judged that the instrumental analysis conditions and preparation method used in this study were valid. The rapid analytical method developed herein could be implemented in many laboratories that seek to save time and labor.