【作者】 韩宝武；

【导师】 范必威；

【作者基本信息】 成都理工大学 ， 分析化学， 2008， 硕士

【摘要】 四环素类抗生素以及磺胺类抗生素已经被广泛应用于预防和治疗食源性动物的疾病,然而过量地使用这些抗生素会导致其在食源性动物产品中的残留,不仅可能污染环境,严重的还可能影响到人类的身体健康,因此,建立一种快速简便的检测动物源性食品中四环素类抗生素及磺胺类抗生素多残留的方法是非常必要的。本研究采用多壁碳纳米管作为一种新型的固相萃取吸附剂自制了固相萃取柱,建立了离线固相萃取的前处理方法对牛奶样品进行前处理,并采用高效液相色谱-质谱联用技术和高效液相色谱法作为检测牛奶中四环素和磺胺类抗生素残留量的分析方法,并且应用所建立的方法对成都市市售的几种牛奶样品进行了检测。本文以多壁碳纳米管作为固相萃取吸附剂建立了牛奶中四环素类抗生素以及磺胺类抗生素残留的固相萃取-液/质联用检测方法。四环素类抗生素的检测采用Agilent TC C18色谱柱进行色谱分离,A:甲醇:乙腈=1:3(V/V),B:0.01mol/L草酸溶液。A:B=4:6(V/V)作为流动相,流速为0.7mL/min;磺胺类抗生素的检测采用大连依利特YWG C18色谱柱进行色谱分离,0.1%甲酸的水溶液:0.1%甲酸的乙腈溶液(68∶32 V/V)作为流动相,流速为1.0mL/min。两种待测抗生素的线性范围分别为0.1～2.0μg/mL和0.05～1.0μg/mL。本文采用液液萃取结合固相萃取作为样品前处理方法,对于牛奶样品中四环素类抗生素的检测,采用购自深圳纳米港有限公司的未经浓硝酸氧化处理的多壁碳纳米管(碳纳米管1)作为固相萃取的吸附剂进行前处理,对于磺胺类抗生素的检测,分别采用经过浓硝酸氧化前后的多壁碳纳米管作为固相萃取吸附剂进行样品前处理。对于牛奶样品中磺胺类抗生素的检测,分别采用碳纳米管1(未经氧化处理的)和碳纳米管2(经过氧化处理的)对样品进行萃取净化,方法回收率分别为70.1%～109.8%和83.3%～110.0%,最后确定使用经过氧化处理的多壁碳纳米管作为固相萃取吸附剂进行样品前处理。该方法检出限0.3μg/L～0.9μg/L,方法精密度4.38%～10.13%,并且采用液质联用对牛奶样品中残留磺胺类抗生素进行检测,探讨了高效液相色谱以及质谱的最佳操作条件。方法检出限远低于欧盟最大残留量的要求。对于牛奶中四环素类抗生素的检测,本文建立的多壁碳纳米管作为固相萃取的前处理方法回收率在94.4%～101.2%之间,方法检出限0.05mg/L,方法精密度为1.9%～5.0%,并且采用高效液相色谱对牛奶样品中残留的四环素类抗生素进行检测,探讨了高效液相色谱的最佳操作条件。本方法精确可靠,灵敏度高,适用于牛奶中四环素及磺胺类抗生素的定量和确认分析。另外,本研究所建立的离线前处理方法与在线仪器相比虽然较为耗时,但是仍然具有一定的实用价值。更多还原

【Abstract】 Tetracycline antibiotics and sulfa antibiotics has been widely used in the prevention and treatment of food-borne animal diseases, but excessive use of these antibiotics will result in food-borne residues in animal products, may not only pollute the environment, serious Also likely to affect human health, therefore, the establishment of a quick and easy way to detect animal-derived food in the tetracycline class antibiotics and sulfa antibiotic residues in many ways is very necessary. This study used multi-walled carbon nanotubes as a new type of solid-phase extraction adsorbent to make a solid phase extraction columns, a solid-phase extraction of offline pre-treatment methods on milk samples before processing and use of high-performance liquid color Spectrum-using mass spectrometry technology and high-performance liquid chromatography as a test of milk in the antibiotics tetracycline and sulfonamides residues in the analysis, and application of the method established by the Chengdu Commercial Several milk samples Were detected.In this paper, a solid-phase extraction-liquid/mass spectrometry detection method which multi-walled carbon nanotubes was used as a solid-phase extraction adsorbent to detect tetracycline antibiotics and sulfa antibiotic residues in milk. Agilent TC C18 column chromatography was used to detection tetracycline antibiotics in milk, A:methanol:acetonitrile=1:3(V/V), B:0.01mol/L oxalic acid solution. A:B=4:6 (V/V) as flow phase; flow rate was 0.7 mL/min; sulfa antibiotics detected by Dalian Gbadolite YWG C18 column for chromatography, flow phase:0.1% formic acid solution: 0.1% formic acid solution of acetonitrile (68:32 V/V); flow rate was 1.0 mL/min. The linear range of two kind of antibiotics under test were 0.1-2.0μg/mL and 0.05-1.0μg/mL. In this paper, liquid-liquid extraction and solid-phase extraction were used as a sample pre-treatment methods, the milk samples, nano-purchased from Shenzhen Co., Ltd. of Hong Kong without a concentrated nitric acid oxidation of the multi-walled carbon nanotubes ( Carbon Nanotubes 1) were used for solid-phase extraction in the detection of tetracycline antibiotics in milk samples, In sulfa antibiotics testing, multi-walled carbon nanotubes before and after the concentrated nitric acid oxidation were used as a solid-phase extraction absorbent sample pre-treatment.The milk samples sulfa antibiotics testing, were used carbon nanotubes 1 (without the oxidation process) and carbon nanotubes 2 (after the oxidation process) on the sample extraction purification, recoveries were 70.1%-109.8% and 83.3% -110.0%, after the finalization of the use of multi-walled carbon nanotubes with a solid-phase extraction absorbent sample pre-treatment. The method detection limit of 0.3μg/L-0.9μg/L, the precision of the method was 4.38%-10.13%, and the sulfa antibiotic residues in milk samples were detected with a method of high-performance liquid chromatography and MS and the best operating conditions was discussed. The detection limits was well below the EU maximum residue requirements.For determination of tetracycline antibiotics in milk, the recovery of the method established in this paper which multi-walled carbon nanotubes was used as a solid-phase extraction absorbent was 94.4%-101.2% and the detection limit was 0.05 mg/L, he precision of the method was 1.9%-5.0%, and high-performance liquid chromatography was used to detect the tetracycline antibiotic residues in milk samples, a high-performance liquid chromatography of the best operating conditions was discussed.The detection of tetracycline and sulfa antibiotics in several milk samples sold in Chengdu was determined by the method of multi-walled carbon nanotubes SPE-LC/MS which was established in this research.更多还原