연구보문 : 환경화학 ; MSPD와 HPLC를 이용한 돼지고기 및 광어 중의 테트라싸이클린계 항생제와 sulfonamide의 다성분 잔류분석법 개발

길근환 ( Geun Hwan Gil ),고광용 ( Kwang Yong Ko ),이용재 ( Yong Jae Lee ),박혜진 ( Hye Jin Park ),이규승 ( Kyu Seung Lee ) 韓國環境農學會 2009 한국환경농학회지 Vol.28 No.3

HPLC를 이용한 분석은 항균, 항생제의 정량분석에 있어 가장 널리 이용되고 있으며, 최근에 개발된 MSPD방법은 고정상을 직접 갈아서 추출, 정제하는 방법으로 전처리 시 그 조작이 간단하며, 유기용매가 적게 들고 전처리 시간이 짧다는 장점이 있다. 본 연구는 HPLC와 MSPD방법을 이용하여 가축 중 소비량이 가장 많은 돼지고기와 생선 중 회로 가장 많이 소비되는 광어에 대하여, 식품 중 잔류 가능성이 높은 tetracycline계 항생제 3종(oxytetracycline, tetracycline, chlortetracycline)과 sulfonamide(sulfadimethoxine, sulfamerazine, sulfamethazine, slfaquinoxaline, sulfamonomethoxine) 5종의 동시분석방법을 개발코자 하였다. HPLC의 최적 분석조건으로 파장은 tetracycline계 항생물질은 360 nm에서 sulfonamide는 270 nm였으며, 이동상은 TC와 SMR이 분리되는 시점인 15분까지는 pH 4.5, oxalic acid: acetonitrile (78.5: 21.5, v/v)로 분석하고 이후 30분까지는 pH 6.1, oxalic acid: acetonitrile (78.5: 21.5, v/v)로 분석을 실시하였을 때 기존의 실험방법보다 피크의 분리도와 검출한계의 개선이 이루어졌으며 이를 토대로 8가지 성분의 MRLs인 0.1~0.2 mg.kg-1까지 충분히 분석이 가능하였다. MSPD 적용을 위한 시료의 전처리 방법개선은 기존의 0.5 g으로 제한된 시료량을 3 g으로 늘릴 수 있었고 dichloromethane 20 mL와 methanol 20 mL로 연속적으로 8가지 성분을 동시에 용출시켜 sulfonamide는 80.25~101.25%, tetracycline계 항생물질은 85.77~121.42%의 회수율을 얻을 수 있었다. This study was conducted to develop more convenient simultaneous determination method by matrix solid phase dispersion (MSPD) and HPLC for sulfonamides such as sulfamerazine (SMR), sulfamethazine (SMT), sulfamonomethoxine (SMM), sulfadimethoxine (SDM), sulfaquinoxaline (SQX), and tetracyclines including oxytetracycline (OTC), tetracycline (TC) chlortetracycline (CTC) in prok and flatfish. The limits of detection were 0.047 mg·kg-1 for OTC, TC, SMR, SMT and SMM, and 0.033 mg·kg-1 for CTC, SDM, and SQX, respectively. So it is sufficiently possible to detect the eight tetracyclines and sulfonamides under their MRLs (0.1~0.2 mg.kg-1). The average percentage recoveries of sulfonamides and tetracyclines from pig muscle and flatfish spiked standard solution were approximately 80.25~101.25% and 85.77~121.42%, respectively. Therefore this method was efficient for simultaneous analysis of eight tetracyclines and sulfonamides.

Fluorescamine을 이용한 sulfonamide의 형광 분석법

임재영,한수남,이문한,박종명,Lim, Jae-young,Han, Su-nam,Lee, Mun-han,Park, Jong-myung 대한수의학회 1990 大韓獸醫學會誌 Vol.30 No.1

These experiments were carried out to develop a novel, simple, and rapid method to determine urinary sulfonamides using fluorescamine by spectrofluorometry. To get optimal conditions for the sulfonamide-fluorescamine reaction, sulfonamides such as sulfamethazine, sulfamerazine, sulfadimethoxine and sulfamonomethoxine, dissolved in buffers with various pH ranges were reacted with various concentrations of fluorescamine. and then, the fluorescence intensity and stability of the fluorophore were measured. To eliminate the interfering substances in urine, the fluorophore in buffers and urine with a definite pH range was extracted with some organic solvents. After then the fluorescence intensity was measured in organic and aquous phases. The results obtained were summarized as follows: 1. The maximal fluorescence of sulfonamides was presented in acidic state, pH 4.5~5.0, at 30 minutes after reaction. 2. The optimal concentration ratio of sulfamethazine and ffuorescamine was more than 1 : 40 in mole. 3. In pH 4.0, the intensity was maximal but was time-dependent, whereas in pH 8.0, the intensity was time-independent. 4. Sulfamethazine-fluorescamine conjugate could be dissolved in some of organic solvents in acidic state such as chloroform, n-butanol, and ethylacetate. 5. Sulfamethazine-flnorescamine conjugate in swine urine coule be extracted with ethylacetate in acidic state, pH 4.0~5.0.

A flexible imprinted photonic resin film templated by nanocrystalline cellulose for naked-eye recognition of sulfonamides

Fusheng Zhang,Enxiu Liu,Xudong Zheng,Longbao Yu,Yongsheng Yan 한국공업화학회 2018 Journal of Industrial and Engineering Chemistry Vol.58 No.-

An optical sulfonamides sensor is fabricated based on a molecular imprinted resin templated bynanocrystalline cellulose. A chiral nematic imprinted compositefilm is synthesized which issubsequently treated with removal of templates to generate a red reflecting photonicfilm. Thefilmshows a naked-eye color response to sulfanilamide, which is related to reassemble imprinted sites in thechiral nematic structure, resulting in a yellow reflectingfilm. Upon exposure to various antibiotics, it canbe simultaneously in selectively response to three sulfonamides. This strategy facilitates enormouslypotential application of the resin as battery-free and portative optical monitoring sensors.

Electronically tuned sulfonamide-based probes with ultra-sensitivity for Ga³⁺ or Al³⁺ detection in aqueous solution

Kumar, A.,Chae, P.S. Elsevier Pub. Co 2017 Analytica chimica acta Vol.958 No.-

<P>Three electronically tuned fluorescent probes (1-3) were synthesized by conjugating a fluorescent unit to N,N-bis-(hydroxyethyl)ethylenediamine. Probe 1 bearing an electron-deficient naphthalenedimide unit did not give a fluorescence response to the presence of various metal ions including monovalent metal ions (Na+, K+, and Ag+), divalent metal ions (Ca2+, Cd2+, Co2+, Ni2+, Cu2+, Hg2+, Pb2+, and Zn2+) and trivalent metal ions (Al3+, Ga3+, Fe3+, and Cr3+) in an aqueous solution. By contrast, probes 2 and 3 possessing 1,8-naphthalimide and pyrene fluorophores, respectively, exhibited selective fluorescent 'OFF-ON' behaviors as a result of Ga3+/Al3+ binding among the diverse metal ions, suggesting the importance of fluorophore electronic character with regard to metal ion sensing. The ethylenediamine analog of probe 3, corresponding to probe 4, was unable to yield a significant change in fluorescence intensity in the presence of any metal ions tested here, revealing the essential role of two hydroxyl groups for metal ion binding. A high association constant of Ka = 2.99 x 10(5) M-1 was obtained for probe 3 with Ga3+, with a limit of detection (LOD) of 10 nM. This LOD is the lowest value known for Ga3+ detection using chemical sensors. Along with an increase in aggregate sizes, PET suppression of probes upon metal ion binding was the primary contributor to the enhancement in fluorescence emission necessary for the sensitive detection of the target ions. The probe-metal ion complexes were fully characterized via TEM, FE-SEM, H-1 NMR, fluorescence spectroscopy techniques and DFT calculations. (C) 2016 Elsevier B.V. All rights reserved.</P>

HPLC를 이용한 원유중 잔류 Sulfonamides 분석법 연구

정동수 ( Dong Su Chung ),윤교복 ( Kyo Bok Yoon ),김종술 ( Jong Sool Kim ),신명균 ( Myung Kyun Shin ),김교승 ( Kyo Seung Kim ) 한국가축위생학회 1993 韓國家畜衛生學會誌 Vol.16 No.1

This experiment was carried out to detect the residues of sulfonamides in raw milk. Raw milks which does not contain sulfonamides was collected from one of the farm and fortified with 5 sulfonamides(sulfamerazine, sulfamethazine, sulfamonomethoxine, sulfadimethoxine, sulfaqinoxaline). The sulfonamides in the fortified sample were extracted and detected by High Performance Liquid Chromatography. UV/vis detector was used in this experiment. The results obtained were summarized as follows: 1. Chloroform was good as a extracting solution. 2. 15.5% methanol in PDP as a mobile phase solution was best detective condition for SMR, SMT, SMM. But for SDM and SQN the best condition was 23% methanol. 3. The detectable limits of SMR, SMT, SMM were 2ppb. but SDM and SQN were 20ppb because of delayed retention time and relatively low recovery rate. 4. The peaks of SMR, SMT, SMM and SDM were erected at baseline and the apexes were sharp but SQN was round shape.

마우스 근육내 설파제 잔류량조사 및 동시분석파장 연구

정경태 ( Kyung Tae Chung ),조헌호 ( Hyun Ho Cho ),이강록 ( Gang Rog Lee ),이우원 ( Woo Won Lee ),양주 ( Ju Yang ),김근규 ( Geun Kyu Kim ) 한국가축위생학회 1999 韓國家畜衛生學會誌 Vol.21 No.4

This survey was carried out to determine 5 residual sulfonamides(sulfamerazine: SMR, sulfa-methazine: SMT, sulfamonomethoxine: SMM, sulfadimethoxine: SDM, sulfaquinoxaline SQX) in muscle of mouse. For this investigation, pertaining detection wavelength, residual levels and residual times in muscle of mouse were summarized as follows; 1. Pertaining detection wavelength of 5 residual sulfonamides(SMR, SMT, SMM, SDM, SQX) was 270nm by HPLC/UV detection. 2. After 1 day put a stop to sulfonamides administration, residual levels was 1~1.5ppm, but were not detected at day 7. 3. Withdrawal time of 5 sulfonamides were about 7 days suspectly.

Cytotoxicities and Quantitative Structure Activity Relationships of B13 Sulfonamides in HT-29 and A549 Cells

Seul Ki Chan Lee,Sang Min Park,Chaeuk Im 대한생리학회-대한약리학회 2011 The Korean Journal of Physiology & Pharmacology Vol.15 No.6

B13 analogues are being considered as therapeutic agents for cancer cells, since B13 is a ceramide analogue and inhibits ceramidase to promote apoptosis in cancer cells. B13 sulfonamides are assumed to have biological activity similar to B13, since they are made by bioisosterically substituting the carboxyl moiety of B13 with sulfone group. Twenty B13 sulfonamides were evaluated for their in vitro cytotoxicities against human colon cancer HT-29 and lung cancer A549 cell lines using MTT assays. Replacement of the amide group with a sulfonamide group increased cytotoxicity in both cancer cell lines. The sulfonamides with long alkyl chains exhibited activities two to three times more potent than that of B13 and compound (15) had the most potent activity with IC₅₀ values of 27 and 28.7ՌM for HT-29 and A549, respectively. The comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) were used to carry out QSAR molecular modeling of these compounds. The predictive CoMSIA models for HT-29 and A549 gave cross-validated q2 values of 0.703 and 0.830, respectively. From graphical analysis of these models, we suppose that the stereochemistry of 1,3-propandiol is not important for activity and that introduction of a sulfonamide group and long alkyl chains into B13 can increase cytotoxicity.

Cytotoxicities and Quantitative Structure Activity Relationships of B13 Sulfonamides in HT-29 and A549 Cells

Lee, Seul Ki-Chan,Park, Sang-Min,Im, Chae-Uk The Korean Society of Pharmacology 2011 The Korean Journal of Physiology & Pharmacology Vol.15 No.6

B13 analogues are being considered as therapeutic agents for cancer cells, since B13 is a ceramide analogue and inhibits ceramidase to promote apoptosis in cancer cells. B13 sulfonamides are assumed to have biological activity similar to B13, since they are made by bioisosterically substituting the carboxyl moiety of B13 with sulfone group. Twenty B13 sulfonamides were evaluated for their in vitro cytotoxicities against human colon cancer HT-29 and lung cancer A549 cell lines using MTT assays. Replacement of the amide group with a sulfonamide group increased cytotoxicity in both cancer cell lines. The sulfonamides with long alkyl chains exhibited activities two to three times more potent than that of B13 and compound (15) had the most potent activity with $IC_{50}$ values of 27 and $28.7{\mu}M$ for HT-29 and A549, respectively. The comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) were used to carry out QSAR molecular modeling of these compounds. The predictive CoMSIA models for HT-29 and A549 gave cross-validated q2 values of 0.703 and 0.830, respectively. From graphical analysis of these models, we suppose that the stereochemistry of 1,3-propandiol is not important for activity and that introduction of a sulfonamide group and long alkyl chains into B13 can increase cytotoxicity.

Determination of Sulfonamides in Meat by Liquid Chromatography Coupled with Atmospheric Pressure Chemical Ionization Mass Spectrometry

Kim, Dal-Ho,Choi, Jong-Oh,Kim, Jin-Seog,Lee, Dae-Woon Korean Chemical Society 2002 Bulletin of the Korean Chemical Society Vol.23 No.11

Liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) has been used for the determination of sulfonamides in meat. Five typical sulfonamides were selected as target compounds, and beef meat was selected as a matrix sample. As internal standards, sulfapyridine and isotope labeled sulfamethazine (${13}^C_6$-SMZ) were used. Compared to the results of recent reports, our result have shown improved precision to a RSD of 1.8% for the determination of sulfamethazine spiked with 75 ng/g level in meat.

경기남부지역 원유중의 설파제 잔류조사

김창수 ( Chang Soo Kim ),이성권 ( Sung Kwon Lee ),고태오 ( Tae Oh Ko ),고신일 ( Sin Il Ko ) 한국가축위생학회 1996 韓國家畜衛生學會誌 Vol.19 No.1

Sulfonamides are widely used to treat mastitis of cattle in field. The study was carried out to analyze sulfonamid residues in raw milk from south Kyeonggi area. The milk sample was deproteinated with acetone and defatted with hexane. The residual sulfonamides were extracted with ethylacetate, concentrated under vaccum, reconstituted with the acetate buffer-methanol mixture, reacted with fluorescamine, and then analyzed by HPLC-fluorescence detector(EX. 395nm, Em. 495nm) with methanol: acetate buffer system(3/2, v/v) as a mobile phase. The results analyzed by Thin layer chromatography and High performance liquid chromatography were summarized as follows. 1. A total of 24 cases out of 478 raw milk samples (5.0%) collected during April and May showed positive reaction to sulfonamide residues. Among 24 positive reactors, 9 cases were positive to sulfanilamides(32.1%), 8 cases were positive to sulfathiazoles(28.6%) and 5 cases were positive to sulfamonomthoxines(7.9%), respectively. 2. During July and August, 31 cases out of 464 raw milk samples(6.7%) showed positive reaction to sulfonamide residues. Among them 5 cases were positive to sulfanilamides, 5 cases sulfathiazoles, and 5 cases sulfamonomethoxines(16.1%), respectively.