• 약학회지
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• 제52권2호
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• pp.137-146
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• 2008

Even though driving under the influence of drug (DUID) is a worldwide problem, we, Korea has no regulation system yet except for alcohol, and there are little cases reported related to DUID. In order to investigate the type of abused drugs for drivers in Korea, we tried to analyze controlled and non-controlled drugs in alcohol-positive blood samples. 275 whole bloods, which were positive for alcohol on the roadside test, were collected from the police for two months ($Nov.{\sim}Dec.$ 2006). The analytical strategy was constituted of three steps: First, alcohol in blood samples were confirmed and quantified by gas chromatography. Second, controlled drugs were screened by $Evidence_{investigator}\;^{TM}$ (Randox, U.K.) as preliminary test. It was based on immunoassay by biochip array analyzer. Nine groups of drug abuse were screened: amphetamines, methamphetamines, cannabis, cocaine, opiates, barbiturates, methadone, benzodiazepines I (oxazepam) & II (lorazepam). Finally, confirmation of these drugs was performed by GC-MS. Blood samples were extracted by solid-phase extraction by $RapidTrace^{TM}$ (Zymark, U.S.A.). After trimethylsilyl (TMS) derivatization, eluates were analyzed to GC-MS. Total 49 drugs were investigated in this study including controlled drugs, antidepressants, 1st generation antihistamines, dextromethorphan, nalbuphine, ketamine, etc. For rapid detection, we developed the automated identification system. It was made up a new software, "DrugMan", modified Chemstation data analysis menu and newly developed macro modules. A series of peak selection, identification and reporting of the results were performed automatically by this system. Concentrations of alcohol in 275 blood samples were ranged from 0.011 to 0.249% (average, 0.119%). Among 149 blood samples, just six samples (4.0%) were showed positive results to the immunoassay: one methamphetamine and five benzodiazepines group I. By GC-MS confirmation, only benzodiazepines were detected and methamphetamine was not detected from immunoassay positive blood sample. Besides these drugs, 5 chlorpheniramines, dextromethorphan, diazepam, doxylamine, ibuprofen, lidocaine and topiramate were also detected in whole bloods by GC-MS. Conclusively, the frequency of drug abuse for Korean drivers was relatively low. There was none case which illegal drug was detected. However these results were limited to alcohol positive blood samples, so it is necessary to analyze more samples including alcohol negative blood.

• 한국토양비료학회지
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• 제45권6호
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• pp.867-876
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• 2012

The concentration of veterinary antibiotics in aqueous and sediment matrices was measured in agricultural irrigation ditches bordering several animal-feeding operations (AFOs) and then compared to its concentration in the watershed. Analytical determination in aqueous samples was based on solid phase extraction (SPE) and appropriate buffer solutions were used to extract residuals in sediment samples. Separation and detection of extracted veterinary antibiotics were performed with high performance liquid chromatograph tandem mass spectrometry (HPLC/MS/MS). In general, higher concentrations of antibiotic were observed in the aqueous phase of irrigation ditches, with the highest concentration of erythromycin hydrochloride (ETM-$H_2O$) of $0.53{\mu}g\;L^{-1}$, than in aqueous watershed samples. In contrast, higher concentrations were measured in river sediment than in irrigation ditch sediment with the highest concentration of oxytetracycline of $110.9{\mu}g\;kg^{-1}$. There was a high calculated correlation ( > 0.95) between precipitation and measured concentration in aqueous samples from the irrigation ditches for five of the ten targeted veterinary antibiotics, indicating that surface runoff could be an important transport mechanism of veterinary antibiotics from field to environment. Further, environmental loading calculation based on measured concentrations in aqueous samples and flow information clearly showed that irrigation ditches were 18 times greater than river. This result suggests the likelihood that veterinary antibiotics can be transported via irrigation ditches to the watershed. The transport via surface runoff and likely environmental loading via irrigation ditches examined in this study helps identify the pathway of veterinary antibiotics residuals in the environment.

• 한국동물위생학회지
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• 제28권3호
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• pp.203-213
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• 2005

Oxytetracycline, tetracycline, chlortetracycline and doxycycline in honey were separated by solid phase extraction (SPE) and determined with high performance liquid chromatography (HPLC) with UV/Visible detector. Analysis was carried out using following conditions: XTerra $C_8$ column $(3.9\times150mm\;i.d. 5{\mu}m)$, mobile phase composed of 0.01M oxalic acid : methanol : acetonitrile (820 : 80 : 100, v/v/v), isocratic pump at a flow rate of 0.9 ml/min. and $50{\mu}l$ of injection volume, UV/Visible detector with wavelength of 360nm. The calibration curves of four tetracyclines showed linearity $(\gamma^2>0.999)$ at concentration range of $100\~1,000 ng/ml$. The recoveries in fortified honey represented more than $70\%$ with low coefficient of variation $(<10\%)$ for concentration range of four tetracyclines. The detection limits for oxytetracycline, tetracycline, chlortetracycline and doxycycline were 13.8, 14.6, 26.2 and 24.9ng/g in acacia honey. respectively. We also monitored tetracyclines residue in domestic honey [n : 38, acacia (20), wild flower (18) ] and foreign honey [n=22, legally distributed (13), illegally distributed (9)] using modified Charm II screening and HPLC confirmation methods. Seven of the 60 samples $(11.7\%)$ were suspect positive using modified Charm II screening test. Chlortetracycline residue was found in one foreign honey (illegally distributed) tested at concentrations of 0.22 ppm. Conclusively, for more effective control of tetracyclines used in beekeeping should be further survey for residues in honey and also national guidelines (maximum residue limit : MRL) and methods should be obligatory.

• 대한화학회지
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• 제55권4호
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• pp.626-632
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• 2011

폭심(phoxim)은 널리 사용되고 있는 구충제인 동물용의약품이다. 본 논문에서는 소와 돼지 근육에 잔류하는 폭심을 분석하기 위해서, 실리카 고체상과 아세토니트릴을 사용하여 추출/정제하였다. 분석을 위해서 LC/ESI-MS/MS 방법이 사용되었다. HPLC에서 $C_{18}$ 컬럼($2.1{\times}100\;mm$, $3.5\;{\mu}m$)이 사용되었으며, 이동상으로는 0.1% formic acid와 물이 사용되었다. 소(0.0048~2.0 mg/kg)와 돼지(0.0055~2.0 mg/kg)에 소량첨가하여 얻은 검정곡선은 좋은 직선성($r^2$=0.995)을 나타내었다. 소와 돼지의 매트릭스에 대해서 0.0048~0.2 mg/kg범위에서 68.2~106.9%의 정확도를 나타내었으며, LOD는 0.0014~0.0017 mg/kg, LOQ는 0.0048~0.0055 mg/kg범위에 있었으며, 11.2%의 상대표준편차를 나타내었다.

• Archives of Pharmacal Research
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• 제28권4호
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• pp.463-468
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• 2005

The purpose of the present study was to develop a standard protocol for imidapril hydrochloride bioequivalence testing. For this reason, a specific LC-MS method was developed and validated for the determination of imidapril in human plasma. A solid-phase extraction cartridge, $Sep-pak^{R}$ C18, was used to extract imidapril and ramipril (an internal standard) from deproteinized plasma. The compounds were separated using a XTerra $MS^{R}$?C18 column ($3.5 {\mu}m, 2.1\times150 mm$) and $acetonitrile-0.1\%$ formic acid (67:33, v/v) adjusted to pH 2.4 by 2 mmol/L ammonium formic acid, as mobile phase at 0.3 mL/min. Imidapril was detected as m/z 406 at a retention time of ca. 2.3 min, and ramipril as m/z 417 at ca. 3.6 min. The described method showed acceptable specificity, linearity from 0.5 to 100 ng/mL, precision (expressed as a relative standard deviation of less than $15\%$), accuracy, and stability. The plasma concentration-versus-time curves of eight healthy male volunteers administered a single dose of imidapril (10 mg), gave an $AUC_{12hr}$ of imidapril of $121.48\pm35.81 ng mL^{-1} h$, and $C_{max} and T_{max}$ values of $32.59\pm9.76 ng/mL and 1.75\pm0.27 h$. The developed method should be useful for the determination of imidapril in plasma with sufficient sensitivity and specificity in bioequivalence study.

• 한국작물학회지
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• 제48권6호
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• pp.429-433
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• 2003

본 연구에서는 땅콩의 resveratrol에 대한 체계적인 연구를 위하여 고속액체크로마토그래피HPLC)를 이용한 땅콩의 trans-resveratrol 분석체계 확립과 품종 및 생육시기별 trans-resveratrol 함량 변화를 구명하여 금후 고부가가치 고함유 기능성 품종개발의 기초 자료로 활용하고자 수행한 결과를 요약하면 다음과 같다. 1. HPLC를 이용한 trans-resveratrol 분석조건은 컬럼은 Xterra $\textrm{C}_{18}$, 이동상 용매조성은 (A) glacial acetic acid DCW(52.6 : 900)과 (B) acetonitril solution A(80:20), 용매흐름속도는 1.1 ml/min, 검출기는 UV-Vis detector 308 nm 이었다. 2. 땅콩에서 trans-resveratrol 추출시 추출용매의 경우 80%EtOH과 80%MeOH이 유의차가 없었고, 추출온도의 경우에도 온도간 유의성이 인정되지 않았으며, ICH guideline에 따른 안전성과 경제성을 고려한 trans-resveratrol의 최적추출 조건은 80% EtOH, $25^{\circ}C$, 45분이었다. 3. 땅콩 품종별 trans-resveratrol 함량 분포범위는 0.018-1.125 $\mu\textrm{g}/\textrm{g}$으로 품종별 유의차가 있었으나, 초형과 립 크기에 따른 trans-resveratrol 함량은 일정한 경향을 보이지 않았다. 4. 종실과 종피를 포함한 종실의 trans-resverarol함량은 종실(0.152-0.305 $\mu\textrm{g}/\textrm{g}$) 보다 종피를 포함한 종실(0.188-0.345 $\mu\textrm{g}/\textrm{g}$)에서 더 높았다. 5. 생육시기별 trans-resveratrol 함량은 신남광땅콩(0.227$\mu\textrm{g}/\textrm{g}$ 대광땅콩(0.418 $\mu\textrm{g}/\textrm{g}$)은 파종 후 110일에 팔광땅콩(0.486 $\mu\textrm{g}/\textrm{g}$)과 밀양16호(0.441 $\mu\textrm{g}/\textrm{g}$)는 파종 후 130일에 가장 높았다.

• 한국환경농학회지
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• 제33권4호
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• pp.381-387
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• 2014

BACKGROUND: Garlic (Allium sativum) extract has been allowed as commercial biopesticide material for pesticidal activity in the Environmentally-friendly Agriculture Promotion Act. Nine commercial biopesticides containing A. sativum extract have been marketed in Korea. However, the analytical method of the active substances in these materials has not been studied. METHODS AND RESULTS: Cartridge clean-up method for the determination of dimethyl disulfide(DMDS), diallyl disulfide(DADS), and diallyl trisulfide(DATS) in biopesticides containing A. sativum extract was developed and validated by gas chromatography(GC). The clean-up method was optimized using hydrophilic lipophilic balance (HLB) solid phase extraction(SPE) cartridges for the bioactive sulfides in biopesticides containing A. sativum extract, and the eluate was analyzed to quantify the DMDS, DADS, and DATS using the GC. The developed method was validated, and the LOQ and recovery rates of DMDS, DADS, and DATS were 0.226, 0.063, and $0.051mg\;L^{-1}$ and 80.6, 84.8, and 73.1%, respectively. From the nine commercial biopesticide samples, contents of DMDS, DADS, and DATS were analyzed using the developed method and results showed $2.3mg\;L^{-1}$, respectively. CONCLUSION: The developed method could be used in determining the quality of biopesticides for the manufacture of commercial biopesticides containing A. sativum extract.

• 한국토양비료학회지
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• 제45권1호
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• pp.43-50
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• 2012

Two typical animal waste management practices, composting and stockpiling, were evaluated for their effect on the degradation of three veterinary antibiotics (VAs), chlortetracycline (CTC), tylosin (TYL), and monensin (MNS). The VAs were applied to horse manure plots subject to composting or stockpiling, and core samples were collected over a period of time. Selected buffer solutions were used to extract the VAs and analysis for concentration was conducted with solid phase extraction (SPE) followed by high performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS) technique. The VAs demonstrated rapid dissipation within ten days followed by a gradual decrease in concentration until the end of the experimental period (141 days). All three VAs degraded more rapidly in the composting samples than in the stockpiling samples, particularly between 20 and 60 days of the observation period. Degradation of the three VAs generally followed a first-order kinetic model, and a fitted model with a calculated rate constant was determined for each treatment. TYL in composting showed the fastest degradation, with a calculated rate constant of $0.91day^{-1}$; the slowest degradation was exhibited by MNS in stockpiling, with rate constant of $0.17day^{-1}$. Calculated correlation coefficients ranged from 0.89 to 0.96, indicating a strong correlation between measured concentrations and fitted values in this study. Although concentration of TYL in composting treatment showed below detection limit during the test period, this study suggests that composting can reduce animal waste contaminants prior to field application as fertilizer.

• 한국자기공명학회논문지
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• 제19권2호
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• pp.67-73
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• 2015

The microcystin is a cyclic heptapeptide from metabolites of cyanobacteria in the genera mycrocystis, anabaeba as a result of eutrophication. It has been known that microcystin-LR is a potent inhibitor of the catalytic subunits of protein phosphatase-1 (PP-1) as well as powerful tumor promoter. The active site of microcystin actually has two metal ions $Fe^{2+}/Zn^{2+}$ close to the nucleophilic portion of PP-1-microcystin complex. We report the isolation and purification of this microcystin-LR from cyanobacteria (blue-green algae) obtained from Daechung Dam in Chung-cheong Do, Korea. Microcystin-LR was extracted from solid-phase extraction (SPE) sample preparation using a CN cartridge. The cyanobacteria extract was purified to obtain microcystin-LR by HPLC method and identified by LC/MS. The detail structural studies that can elucidate the possible role of monovalent and divalent metal ions in PP-1-microcystin complexation were carried out by utilizing molecular dynamics. Conformational changes in metal binding for ligands were monitored by molecular dynamic computation and potential of mean force (PMF) using the method of the free energy perturbation. The microcystin-metal binding PMF simulation results exhibit that microcystin can have very stable binding free energy of -10.95 kcal/mol by adopting the $Mg^{2+}$ ion at broad geometrical distribution of $0.5{\sim}4.5{\AA}$, and show that the $K^+$ ion can form a stable metal complex rather than other monovalent alkali metal ions.

• 한국물환경학회지
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• 제26권3호
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• pp.446-453
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• 2010

This study was investigated nine nitrosamines in small tributary rivers, sewage treatment plants (STPs) and drinking water treatment plants. They are N-nitrosodimethylamine (NDMA), N-nitrosomethylethylamine (NMEA), N-nitrosodiethylamine (NDEA), N-nitrosopyrrolidine (NPYR), N-nitrosodi-n-propylamine (NDPA), N-nitrosomorpholine (NMOR), N-nitrosopiperidine (NPIP), N-nitrosodi-n-butylamine (NDBA) and N-nitrosodiphenylamine (NDPHA). The nine nitrosamines were analyzed by gas chromatography mass spectrometry (GC/MS) using solid phase extraction (SPE) with a coconut charcoal cartridge. Among the nine nitrosamines, NDMA, NMEA, NDEA, NDPA NDBA and NDPHA were detected in small tributary rivers and sewage tretment plants. In small tributary rivers, NDMA, NMEA, NDEA, NDPA, NDBA and NDPHA were obtained as ND~16.4 ng/L, ND~17.7 ng/L, ND~102.4 ng/L, ND~455.4 ng/L, ND~330.1 ng/L and ND~161.0 ng/L, respectively. Also NDMA, NMEA, NDEA, NDPA and NDBA were investigated ND~821.4 ng/L, 22.5~55.4 ng/L, 53.2~588.5 ng/L, ND~56.6 ng/L and ND~527.9 ng/L in STPs, respectively. In drinking water treatment plants, NMEA and NDEA concentration were increased to as high as 38.8 ng/L after ozonation process. However nitrosamines were decreased subsequent biological activated carbon (BAC) treatment process. It was supposed that nitrosamines were formed by $O_3$ oxidation and were removed by biodegradation of BAC.