饲料及生物样品中性激素的四级杆飞行时间质谱分析方法研究
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摘要
性激素是一类由动物体的性腺产生的,具有促进性器官成熟、副性征发育及维持性功能等作用。性激素的结构是一类甾族化合物。性激素的分泌均极微量,其调节作用明显且范围甚广,但它们中的任何一种都不能在体内发动一个新的代谢过程。它们也不直接参与物质或能量的转换,只是直接或间接地促进或减慢体内原有的代谢过程,调节代谢及生理过程的进行速度和方向,从而使机体的活动更适应于内外环境的变化。性激素的代谢失活途径也大致相同,即在肝、肾等代谢器官中形成葡萄糖醛酸酯或硫酸酯等水溶性较强的结合物,然后随尿排出,或随胆汁进入肠道由粪便排出。性激素一般分为雄激素、雌激素和孕激素三大类。
从上世纪八十年代开始,性激素作为可以促进动物生长的药物添加到饲料中,这些药物的使用,对促进动物生长、提高饲料转化率、控制生殖周期及繁殖性能、改善饲料的适口性、提高动物性食品的风味,起到了十分重要的作用。然而,尽管激素添加剂对于畜牧业起到了一定的作用,但在发挥积极作用的同时,性激素及代谢产物也残留在畜禽及其产品中,对人类健康造成危害。人类长期食用含有激素的肉制食品,即使含量甚微,但由于其作用极强,也会明显扰乱机体的激素平衡,导致妇女的更年期紊乱、生育能力下降,新生儿免疫力下降,女童性早熟,男性女性化,男性生殖系统发育异常或引起病变,并导致女性乳腺癌和子宫内膜异位症发生率上升,并且具有强致癌、致畸作用,诱发女性乳腺癌、卵巢癌等疾病,对人体健康极为不利。因此,本文针对饲料和生物样品中添加和残留的性激素进行研究,应用超高效液相色谱串联四级杆飞行时间质谱建立相应的检测方法。
超高效液相色谱串联四级杆飞行时间质谱检测饲料中9种雄性激素方法的建立,是以乙酸乙酯先对饲料样品进行提取,然后用QuEChERS净化方法对上清液净化,即在上清液中加入PSA、C18和无水MgSO4,振荡离心后的上清液经蒸干回溶后进仪器检测。采用正离子模式,流动相为甲醇和0.1%甲酸水溶液,分别对流动相、提取溶剂、QuEChERS方法进行优化,最后,在最优条件下,得到9种雄性激素的方法定量限范围为10-43μg/kg,回收率范围为70.0%～99.7%。本方法准确度明显高于其他分析方法,能够更好地满足欧盟等发达国家和组织对食品中残留药物的定性要求,能够有效避免假阳性结果的出现,在食品安全控制中具有很好的实用性。
超高效液相色谱串联四级杆飞行时间质谱检测尿中的8种雌激素代谢产物方法的建立,是基于通常检测雌激素类药物的方法都需要酶解或衍生,前处理繁琐,而直接检测雌激素类药物的代谢物就可避免这些操作,而且代谢物的质谱响应值比雌激素类药物的响应值要高。本方法直接用C18固相萃取柱净化尿液,采用负离子模式,流动相采用乙腈和0.1%甲酸水溶液,并对固相萃取柱的选择和洗脱液进行优化。本实验的8种雌激素代谢产物的方法定量限范围为5-10μg/kg,回收率范围为80.9～106.7%。本方法前处理简单,准确度高,可有效的应用于食品安全领域。
超高效液相色谱串联四级杆飞行时间质谱检测肌肉中的8种雌激素代谢产物方法的建立,是用甲醇:水(1:1)和甲醇:水(1:4)进行两次提取,提取液用正己烷脱脂,最后用HLB固相萃取柱进行净化,采用负离子模式,以乙腈和0.1%甲酸水溶液作为流动相,并对流动相、提取液、固相萃取柱和洗脱液进行优化。本方法8种雌激素代谢产物的方法定量限范围为5-15μg/kg,回收率范围为76%～98.9%。本方法前处理简单,准确度高,可有效的应用于食品安全领域。
超高效液相色谱串联四级杆飞行时间质谱检测饲料中的6种孕激素方法的建立,先用乙腈提取,再用MCX固相萃取柱进行净化,采用正离子模式,以乙腈和0.1%甲酸水溶液作为流动相,并对流动相、固相萃取柱和洗脱液进行优化。本方法6种孕激素的方法定量限范围为6-10μg/kg,回收率范围为83.1%～104.5%。本方法前处理简单,准确度高,可有效的应用于食品安全领域。
Sex hormones are produced by the animal's gonads, which have a great effect of promoting mature sexual organs, developing secondary sex characteristics and maintaining sexual functions. The structure of sex hormone is a kind of steroid compound. Secretion of sex hormones is a extremely trace amount, but its regulation effect is obvious and wide-ranging, however, any single ingredient in them can not start a new metabolic process in the body. They are not directly involved in the substantial and energetic transformation but directly or indirectly promote or slow down the original metabolic process in the body, adjusting the speed and direction of the metabolism and physiological process in order to make the body more adapted to the internal and external environmental changes. Metabolism inactivation ways of sex hormones are roughly the same, Sex hormones can shape glucuronide or sulfate compound in the liver, kidney and other organs, and then excrete with the urine or feces. Sex hormones are generally divided into three major categories: androgen, estrogen and progestin.
Since 1980s, sex hormones are used to be a additive into the animals’feed to promote the growth of animals, these additives can promote the growth of animal improve the feed conversion, control reproductive cycle and reproductive performance, improve the feed palatability and the animal food flavor. Although the hormones have some effect for animal husbandry, it can also lead the metabolites residue in livestock and poultry products, causing harm to human health. If people eat meat food containing hormones for a long time, even if the content is a trace amount, but the effect is extremely strong, which also can obviously disturb the hormone balance, resulting in women's menopause disorder, fertility decline, decreasing neonatal immunity, girls with sexual precocity, developmental abnormalities or causing lesions of the male reproductive system, leading to the increase in female breast cancer and ovarian endometriosis incidence, it has strong carcinogenic and teratogenic effects, inducing female diseases such as breast cancer and ovarian cancer, and adverse to human health. Thus, this paper have researched for the adding and residual sex hormones in the feed and biological samples, and established corresponding detection methods with ultra-performance liquid chromatography-quadrupole-time-of-flight mass.
The method was established for 9 androgen in feed by ultra-performance liquid chromatography-quadrupole-time-of-flight mass, which extracted by ethyl acetate, then purified the extracting solution by QuEChERS which added the PSA, C18 and MgSO4 to the extracting solution, oscillated and centrifuged, finally the extracting solution was evaporated to dryness under a stream of nitrogen .The residue was dissolved and analyzed on UPLC-QTOF. The method was positive mode, the mobile phase was methanol and 0.1% formic acid-water solution, and the method was optimized for the mobile phase, extraction solution and QuEChERS method. Finally, in the best condition, the limit of quantification of 9 androgen was 10-43μg/kg, and the recovery was 70.0% ~ 99.7% range. This method was much higher than other method in accuracy, and it could better content the qualitative requirement of the residues of drugs in food for the European Union and other developed countries and organizations, and it could effectively avoid false positive results, which had the very good practicability in the food safety control.
The method was established for 8 estrogen metabolites in urine by ultra-performance liquid chromatography-quadrupole-time-of-flight mass. The old methods were required enzymatic or derivative for estrogen drugs, and pretreatment was cumbersome, but the direct detection of metabolites of estrogen drugs could avoid these operations, and the mass response of metabolites was higher than the response of estrogen drugs. This method directly purified the urine with C18 SPE, and was negative mode. The mobile phase was acetonitrile and 0.1% formic acid-water solution, and the method was optimized for the choice and eluent of solid phase extraction column. The limit of quantification of 8 estrogen metabolites was 5-10μg/kg, the recovery range was 80.9%~106.7%.This method had simple pretreatment, high accuracy, and it can be effectively applied in the food safety field.
The method was established for 8 estrogen metabolites in muscle by ultra-performance liquid chromatography-quadrupole-time-of-flight mass, which was extracted twice with methanol: water (1:1) and methanol: water (4:1), and eliminated the fat with hexane from the extraction, finally purified the extraction with HLB SPE. The method was negative mode, the mobile phase was acetonitrile and 0.1% formic acid-water solution, and the method was optimized for the mobile phase, extraction, SPE column and eluent. The limit of quantification of 8 estrogen metabolites was 5-15μg/kg, the recovery range was 76%~ 98.9%.This method had simple pretreatment, high accuracy, and it can be effectively applied in the food safety field.
The method was established for 6 progestin in feeds by ultra-performance liquid chromatography-quadrupole-time-of-flight mass, which was extracted with acetonitrile, and purified with MCX column SPE. The method was positive mode, the mobile phase was acetonitrile and 0.1% formic acid-water solution, and the method was optimized for the mobile phase, SPE column and eluent. The limit of quantification of 6 progestin was 6-10μg/kg, and the recovery range was 83.1%~ 104.5%. This method had simple pretreatment, high accuracy, and it could be effectively applied in the food safety field.
从上世纪八十年代开始,性激素作为可以促进动物生长的药物添加到饲料中,这些药物的使用,对促进动物生长、提高饲料转化率、控制生殖周期及繁殖性能、改善饲料的适口性、提高动物性食品的风味,起到了十分重要的作用。然而,尽管激素添加剂对于畜牧业起到了一定的作用,但在发挥积极作用的同时,性激素及代谢产物也残留在畜禽及其产品中,对人类健康造成危害。人类长期食用含有激素的肉制食品,即使含量甚微,但由于其作用极强,也会明显扰乱机体的激素平衡,导致妇女的更年期紊乱、生育能力下降,新生儿免疫力下降,女童性早熟,男性女性化,男性生殖系统发育异常或引起病变,并导致女性乳腺癌和子宫内膜异位症发生率上升,并且具有强致癌、致畸作用,诱发女性乳腺癌、卵巢癌等疾病,对人体健康极为不利。因此,本文针对饲料和生物样品中添加和残留的性激素进行研究,应用超高效液相色谱串联四级杆飞行时间质谱建立相应的检测方法。
超高效液相色谱串联四级杆飞行时间质谱检测饲料中9种雄性激素方法的建立,是以乙酸乙酯先对饲料样品进行提取,然后用QuEChERS净化方法对上清液净化,即在上清液中加入PSA、C18和无水MgSO4,振荡离心后的上清液经蒸干回溶后进仪器检测。采用正离子模式,流动相为甲醇和0.1%甲酸水溶液,分别对流动相、提取溶剂、QuEChERS方法进行优化,最后,在最优条件下,得到9种雄性激素的方法定量限范围为10-43μg/kg,回收率范围为70.0%～99.7%。本方法准确度明显高于其他分析方法,能够更好地满足欧盟等发达国家和组织对食品中残留药物的定性要求,能够有效避免假阳性结果的出现,在食品安全控制中具有很好的实用性。
超高效液相色谱串联四级杆飞行时间质谱检测尿中的8种雌激素代谢产物方法的建立,是基于通常检测雌激素类药物的方法都需要酶解或衍生,前处理繁琐,而直接检测雌激素类药物的代谢物就可避免这些操作,而且代谢物的质谱响应值比雌激素类药物的响应值要高。本方法直接用C18固相萃取柱净化尿液,采用负离子模式,流动相采用乙腈和0.1%甲酸水溶液,并对固相萃取柱的选择和洗脱液进行优化。本实验的8种雌激素代谢产物的方法定量限范围为5-10μg/kg,回收率范围为80.9～106.7%。本方法前处理简单,准确度高,可有效的应用于食品安全领域。
超高效液相色谱串联四级杆飞行时间质谱检测肌肉中的8种雌激素代谢产物方法的建立,是用甲醇:水(1:1)和甲醇:水(1:4)进行两次提取,提取液用正己烷脱脂,最后用HLB固相萃取柱进行净化,采用负离子模式,以乙腈和0.1%甲酸水溶液作为流动相,并对流动相、提取液、固相萃取柱和洗脱液进行优化。本方法8种雌激素代谢产物的方法定量限范围为5-15μg/kg,回收率范围为76%～98.9%。本方法前处理简单,准确度高,可有效的应用于食品安全领域。
超高效液相色谱串联四级杆飞行时间质谱检测饲料中的6种孕激素方法的建立,先用乙腈提取,再用MCX固相萃取柱进行净化,采用正离子模式,以乙腈和0.1%甲酸水溶液作为流动相,并对流动相、固相萃取柱和洗脱液进行优化。本方法6种孕激素的方法定量限范围为6-10μg/kg,回收率范围为83.1%～104.5%。本方法前处理简单,准确度高,可有效的应用于食品安全领域。
Sex hormones are produced by the animal's gonads, which have a great effect of promoting mature sexual organs, developing secondary sex characteristics and maintaining sexual functions. The structure of sex hormone is a kind of steroid compound. Secretion of sex hormones is a extremely trace amount, but its regulation effect is obvious and wide-ranging, however, any single ingredient in them can not start a new metabolic process in the body. They are not directly involved in the substantial and energetic transformation but directly or indirectly promote or slow down the original metabolic process in the body, adjusting the speed and direction of the metabolism and physiological process in order to make the body more adapted to the internal and external environmental changes. Metabolism inactivation ways of sex hormones are roughly the same, Sex hormones can shape glucuronide or sulfate compound in the liver, kidney and other organs, and then excrete with the urine or feces. Sex hormones are generally divided into three major categories: androgen, estrogen and progestin.
Since 1980s, sex hormones are used to be a additive into the animals’feed to promote the growth of animals, these additives can promote the growth of animal improve the feed conversion, control reproductive cycle and reproductive performance, improve the feed palatability and the animal food flavor. Although the hormones have some effect for animal husbandry, it can also lead the metabolites residue in livestock and poultry products, causing harm to human health. If people eat meat food containing hormones for a long time, even if the content is a trace amount, but the effect is extremely strong, which also can obviously disturb the hormone balance, resulting in women's menopause disorder, fertility decline, decreasing neonatal immunity, girls with sexual precocity, developmental abnormalities or causing lesions of the male reproductive system, leading to the increase in female breast cancer and ovarian endometriosis incidence, it has strong carcinogenic and teratogenic effects, inducing female diseases such as breast cancer and ovarian cancer, and adverse to human health. Thus, this paper have researched for the adding and residual sex hormones in the feed and biological samples, and established corresponding detection methods with ultra-performance liquid chromatography-quadrupole-time-of-flight mass.
The method was established for 9 androgen in feed by ultra-performance liquid chromatography-quadrupole-time-of-flight mass, which extracted by ethyl acetate, then purified the extracting solution by QuEChERS which added the PSA, C18 and MgSO4 to the extracting solution, oscillated and centrifuged, finally the extracting solution was evaporated to dryness under a stream of nitrogen .The residue was dissolved and analyzed on UPLC-QTOF. The method was positive mode, the mobile phase was methanol and 0.1% formic acid-water solution, and the method was optimized for the mobile phase, extraction solution and QuEChERS method. Finally, in the best condition, the limit of quantification of 9 androgen was 10-43μg/kg, and the recovery was 70.0% ~ 99.7% range. This method was much higher than other method in accuracy, and it could better content the qualitative requirement of the residues of drugs in food for the European Union and other developed countries and organizations, and it could effectively avoid false positive results, which had the very good practicability in the food safety control.
The method was established for 8 estrogen metabolites in urine by ultra-performance liquid chromatography-quadrupole-time-of-flight mass. The old methods were required enzymatic or derivative for estrogen drugs, and pretreatment was cumbersome, but the direct detection of metabolites of estrogen drugs could avoid these operations, and the mass response of metabolites was higher than the response of estrogen drugs. This method directly purified the urine with C18 SPE, and was negative mode. The mobile phase was acetonitrile and 0.1% formic acid-water solution, and the method was optimized for the choice and eluent of solid phase extraction column. The limit of quantification of 8 estrogen metabolites was 5-10μg/kg, the recovery range was 80.9%~106.7%.This method had simple pretreatment, high accuracy, and it can be effectively applied in the food safety field.
The method was established for 8 estrogen metabolites in muscle by ultra-performance liquid chromatography-quadrupole-time-of-flight mass, which was extracted twice with methanol: water (1:1) and methanol: water (4:1), and eliminated the fat with hexane from the extraction, finally purified the extraction with HLB SPE. The method was negative mode, the mobile phase was acetonitrile and 0.1% formic acid-water solution, and the method was optimized for the mobile phase, extraction, SPE column and eluent. The limit of quantification of 8 estrogen metabolites was 5-15μg/kg, the recovery range was 76%~ 98.9%.This method had simple pretreatment, high accuracy, and it can be effectively applied in the food safety field.
The method was established for 6 progestin in feeds by ultra-performance liquid chromatography-quadrupole-time-of-flight mass, which was extracted with acetonitrile, and purified with MCX column SPE. The method was positive mode, the mobile phase was acetonitrile and 0.1% formic acid-water solution, and the method was optimized for the mobile phase, SPE column and eluent. The limit of quantification of 6 progestin was 6-10μg/kg, and the recovery range was 83.1%~ 104.5%. This method had simple pretreatment, high accuracy, and it could be effectively applied in the food safety field.
引文
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