CN111679024A - 一种疏水性低温共融物的制备及萃取肉制品、水产品中刚果红、酸性金黄和红2g的方法 - Google Patents
一种疏水性低温共融物的制备及萃取肉制品、水产品中刚果红、酸性金黄和红2g的方法 Download PDFInfo
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Abstract
本发明公开了一种疏水性低温共融物的制备及萃取肉制品、水产品中刚果红、酸性金黄和红2G的方法,属于食品检测技术领域,以解决传统方法存在步骤繁琐、试剂消耗大、易对人员造成呼吸道损伤等的问题,包括如下步骤,将氢键受体和氢键供体混合,加热至混合物完全变成透明澄清液体,放凉至室温即得,检测方法,包括取干燥的样品,加水超声,离心,取上清液;将疏水性低温共融物及所有上清液混合,涡旋,静置,产生油状液滴,吸取全部该油状液滴,用乙腈溶解并定容,微孔有机滤膜过滤,得滤液;滤液用液质联用仪测定。在保证检出率的情况下,大大提高了检测效率,降低了检测成本,大大简化了试验步骤,该检测方法的适用性和稳定性好。
Description
技术领域
一种疏水性低温共融物的制备及萃取肉制品、水产品中刚果红、酸性金黄和红2G的方法,本发明属于食品检测技术领域,具体涉及肉制品、水产品检测技术领域。
背景技术
由于非法添加工业染料具有价格低、着色强、稳定性强等特点,在经济利益的驱使下,不法商家在产品的生产过程中添加非法工业染料,达到改善色泽、提高品相的目的,进而谋取利益。根据近年国家食品监督抽检细则和风险监测任务看,非法添加工业染料越来越受到关注,肉制品中的刚果红已列为检测项目进行监测。偶氮类染料是由重氮化胺与胺或苯酚耦合而成,并含有一个或多个偶氮键。它们是工业染料中最大的一类(60-70%)。偶氮类染料可与机体蛋白结合,为可疑致癌物与诱变剂。进入人体后,在正常代谢条件下,可能发生偶氮基断裂,生成致癌芳香胺,并经过活化作用改变人体DNA的结构与功能,引起病变和诱发癌症。刚果红属于联苯胺为母体的红色偶氮染料,一般应用于纺织印染、造纸、临床诊断、生物染色剂及酸碱指示剂等。不法商贩常用刚果红对肉制品进行着色,它不仅在食物中有残留,在生产和使用过程中也容易进入水体,对环境造成危害。酸性金黄属于偶氮类工业染料,主要用于腈纶、家具、纸张、纺织品、皮革及化妆品的染色,其在中性条件下与蛋白质有较强的吸附作用,比食用色素更易染色,而且色泽鲜艳不易褪色。不法商贩常用豆制品、蜜饯、辣椒制品、黄鱼等食品着色。红2G是一种红色单偶氮染料,主要用于羊毛织物的染色。不法商贩常用于香肠、海鲜酱、辣酱等食品的着色。目前已有检测方法存在步骤繁琐、耗时长、损失大、试剂消耗大、易对人员造成呼吸道损伤等缺点。
目前检测这三种非法添加染料的方法有:液液萃取-LCTOF法,液液萃取-LCMS法,GPC-LCTOF法,固相萃取-LCMS法,单扫描极谱法,固相萃取-LC法等。
上述传统方法均存在步骤繁琐、耗时长、损失大、试剂消耗大、易对人员造成呼吸道损伤等缺点。
发明内容
本发明的目的在于:提供一种疏水性低温共融物的制备及萃取肉制品、水产品中刚果红、酸性金黄和红2G的方法,以解决上述传统方法存在步骤繁琐、试剂消耗大、易对人员造成呼吸道损伤等的问题。
本发明采用的技术方案如下:
一种疏水性低温共融物的制备方法,包括如下步骤,将氢键受体和氢键供体混合,加热至混合物完全变成透明澄清液体,放凉至室温即得。
本申请的技术方案中,选择不同的氢键供体和氢键受体合成多种疏水性低温共融物,以该疏水性低温共融物作为萃取剂,只需要添加微量的疏水性低温共融物,就可萃取样品中的目标物,在保证检出率的情况下,大大提高了检测效率,降低了检测成本,大大简化了试验步骤,该检测方法的适用性和稳定性好。
优选的,所述氢键受体包括四丁基氯化铵、1-乙基-3-甲基咪唑氯盐、1-己基-3-甲基咪唑氯盐中的任一种。
优选的,所述氢键供体包括正辛酸或正癸酸。
优选的,氢键受体与氢键供体的摩尔比为1:1-1:3。
更为优选的,氢键受体与氢键供体的摩尔比为1:2。
优选的,50-60℃的油浴加热25-35分钟。
优选的,55℃的油浴加热30分钟。
一种疏水性低温共融物的制备方法获得的疏水性低温共融物。
一种肉制品、水产品中三种非法添加工业染料的检测方法,包括如下步骤:
步骤1、取干燥的样品,加水超声,离心,取上清液;
步骤2、将疏水性低温共融物及所有上清液混合,涡旋,静置,产生油状液滴,吸取全部该油状液滴,用乙腈溶解并定容,微孔有机滤膜过滤,得滤液;
步骤3、滤液用液质联用仪测定
优选的,步骤1样品包括肉制品或水产品,肉制品取肌肉部分,水产品取皮和肉部分,均质干燥得干燥的样品;样品g与水mL的料液比为1:2-1:10,超声10min,10000rpm离心5min;步骤2中将50-400μL HDES及所有上清液置入10mL玻璃注射器中,涡旋1-3min,静置2min,产生油状液滴,吸取全部该油状液滴于2mL压盖离心管,用乙腈溶解并定容至1.0mL,过0.45μm微孔有机滤膜。
优选的,步骤1样品g与水mL的料液比为1:5,超声10min,10000rpm离心5min;步骤2中将200μL HDES及所有上清液置入10mL玻璃注射器中,涡旋3min。
试验部分:
1.材料与试剂
CR(德国,CNW)、MY(德国,Dr)、R2G(安谱,上海),四丁基氯化铵、1-乙基-3-甲基咪唑氯盐、1-己基-3-甲基咪唑氯盐(上海,成捷化学)。标准品用甲醇制成储备溶液(1000ug/mL),4℃储存备用。乙酸铵、乙腈为色谱纯(Fisher,美国),正癸酸、正辛酸为分析纯(安谱,上海)。去离子水由GenPure UV-TOC/UF×CAD plus(Thermo,美国)超纯水机制备;选择具有代表性的肉制品、水产品,样品均从超市购买。
2.仪器与设备
高效液相色谱质谱联用仪(ABSciex5500Qtrap);控温磁力搅拌器(IKA,德国);Genius 3涡旋仪(IKA,德国);玻璃注射器(10mL);液相微量进样针(10uL)。
3.色谱条件
色谱柱:ACQUITY UPLCQBEHC18色谱柱(50mm×2.1mm,1.7um,Waters,美国);柱温:40℃;进样体积:5.00uL;流动相:A为5mmol乙酸铵水溶液,B为乙腈,流速为0.3mL/min;梯度程序:20%B保持1min,在2min内线性增加至80%B,保持1min,在
0.1min内线性递减至20%B,保持1.9min。
4.质谱条件
离子源:Electron Spray lonization(ESl);离子化电压:-4500V;辅助加热气压力:55psi;喷雾气压力:50psi;辅助加热气温度:550℃;动态多反应监测(MRM)模式;负离子扫描;3种非法添加染料的质谱参数详见表1。
表1 3种非法添加染料色谱质谱参数
本申请中,CR表示刚果红;MY表示酸性金黄;R2G表示红2G;
HDES疏水性低温共融物。
综上所述,由于采用了上述技术方案,本发明的有益效果是:
1、本发明中,通过选的获得的特异性低温共融物对刚果红、酸性金黄和红2G进行萃取检测,可以大大简化实验步骤,提升实验效率,降低试验成本,保护人员的健康;
2、本发明中,只需要添加微量的疏水性低温共融物,就可萃取样品中的目标物,在保证检出率的情况下,大大提高了检测效率;
3、本发明中,是在原有检测方法基础上,颠覆传统样品前处理步骤,引入新型的绿色溶剂作为萃取剂,大大简化试验步骤,优化各项参数,保证检测方法的适用性及稳定性;
4、本发明中,在同等检测参数下,筛选了吸附刚果红、酸性金黄、红2G的能力最强的疏水性低温共融物HDES-5,优选了在固定含量的刚果红、酸性金黄、红2G,疏水性低温共融物的最小使用体积作为实验参数,优选了疏水性低温共融物与待测液混合时的涡旋时间,保证在该时间内达到最大萃取率,优选了样品与溶剂混合时的料液比,保证在该料液比下,疏水性低温共融物达到最大萃取率;
5、本发明中,采用液质联用仪,重点研究了离子对的去簇电压、碰撞电压、液相色谱流动相等,保证刚果红、酸性金黄、红2G的检测灵敏度最高,检出限最低;
6、本发明的疏水性低温共融物作为一种新型、低毒、绿色的材料,不仅成本低、易合成,而且负载能力强、简便易操作,具有很好的推广价值;
7、本发明通过1-己基-3-甲基咪唑氯盐和正辛酸为原料合成了新型疏水性低温共融物,将其作为溶剂应用到肉制品、水产品中3种非法添加工业染料的提取中,采用LC-MS分析,建立了快速、高效、安全、同时检测肉制品、水产品中3种非法添加工业染料的检测方法。3种非法添加工业染料的定量限范围为0.02~0.88ug/kg,在不同线性范围(1.0~20.0、0.1~2.0ugkg)下相关性良好(R2>0.9944)。3种非法添加工业染料分别进行了3水平标准添加测试,回收率达93.25~101.36%,相对标准偏差为1.27~4.06%。
附图说明
图1为本发明不同HDES对3种非法添加工业染料提取的效果;
图2为本发明HDES的用量对3种非法添加工业染料提取的影响;
图3为本发明涡旋时间对提取率的影响;
图4为本发明料液比对提取率的影响;
图5为本发明3种非法添加工业染料的标准品总离子流图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例1
一种疏水性低温共融物的制备方法,分别称取不同的氢键供体和氢键受体于25mL圆底烧瓶中,在55℃油浴中加热,直到两种混合物完全变成透明澄清液体即可,放凉至室温后备用。疏水性低温共融物合成的氢键受体与氢键供体的配对关系如表2所示。
表2疏水性低温共融物的合成表
实施例2
在实施例1的基础上,一种肉制品、水产品中三种非法添加工业染料的检测方法,包括如下步骤:
步骤1、取干燥的样品,样品g与水mL的料液比为1:5,超声10min,10000rpm离心5min,取上清液,样品包括肉制品或水产品,肉制品取肌肉部分,水产品取皮和肉部分,均质干燥得干燥的样品;
步骤2、将200μL HDES及所有上清液置入10mL玻璃注射器中,涡旋3min,静置2min,产生油状液滴,吸取全部该油状液滴于2mL压盖离心管,用乙腈溶解并定容至1.0mL,过0.45μm微孔有机滤膜,得滤液;
步骤3、滤液用液质联用仪测定。
试验例1
HDES选择:
如图1所示,采用表1中合成的6种疏水性低温共融物对3种非法添加染料进行特异性吸附试验,结果如图1所示。HDES-4对目标物有轻微吸附效果,HDES析出并下沉;HDES-2对刚果红、酸性金黄有明显吸附效果,对红2G吸附效果不明显,HDES析出并上浮;HDES-3对酸性金黄吸附效果明显,对刚果红、红2G无吸附效果;HDES-1、5、6对目标物均有明显吸附,且呈油状液滴浮于水面,课进一步进行测试。HDES-1、5、6的提取效果见图1。由图得出,HDES-5对于三种目标物的提取效率最佳且操作步骤省时,HDES-6提取效率次之,HDES-1提取效率最低。
试验例2
HDES用量考察:
如图2所示,采用不同剂量HDES-5进行测试,考察其对3种非法添加工业染料的提取能力。考虑到在混合加标样品中存在竞争吸附的现象,本试验重点考察针对混合目标物的提取能力。具体数据如图,最终采用200μL作为疏水性低温共融物的最佳用量。
试验例3
涡旋时间的影响:
如图3所示,HDES与待测液的涡旋时间直接影响对目标物质的提取率。本试验将涡旋时间作为重点因素进行考察。本试验采用200μL HDES对同一待测溶液分别选用不同涡旋时间(1.0min、1.5min、2.0min、2.5min、3.0min)进行测试,考察不同目标物的响应情况。如图,三种目标物在提取时间为2min时提取率均大于95%,综上,选择3min作为本试验的最优提取时间。
试验例4
料液比的影响:
如图4所示,样品与溶剂混合时的料液比会直接影响到目标物的提取效率,本试验将料液比作为重点因素进行考察。本试验采用200μL DES对同一待测溶液分别选用不同料液比(1:2,1:3.5,1:5,1:6.5,1:8,1:10)进行测试,考察3种目标物的响应情况,当料液比为1:2时,样品与溶剂混合后呈糊状,加入HDES后不便于提取,当料液比为1:3.5时,三种目标物的提取率均小于60%,当料液比为1:5时,三种目标物的提取率均超过95%,1:6.5,1:8,1:10时提取率并无明显的增加,综上,选择1:5作为本试验的最优料液比。
试验例5
仪器参数优化:由于待测的三个目标物均为负离子模式采集,流动相中添加乙酸铵可以增加目标物的离子化效率,乙腈的使用可以使目标物的峰形更加尖锐。综上,本试验采用5mmol乙酸铵水溶液和乙腈作为流动相进行梯度洗脱。
根据离子对响应高且易获得(碰撞电压相对较低)的原则,各选择2个离子对作为定量、定性离子对。以刚果红为例,当去簇电压从0V~-200V变化时,首先CR的带电粒子与溶剂分析形成的簇离子会随着电压的增强而减少,刚果红加合离子的响应逐步增强,当电压超过一定值后,会发生源内裂解,从而加和离子的响应会明显降低。这个值就是我们需要选择的最优去簇电压。当碰撞电压从0V~-100V变化时,首先刚果红会随着电压的增强而碎裂,特征子离子对的响应逐步增强,当电压超过一定之后,特征子离子会进一步碎裂成孙离子,导致特征子离子响应减弱。这个值就是我们需要选择的最优碰撞电压。综上,选择-120V作为刚果红的最优去簇电压,-30V为定量离子对325.0/152.0的最优碰撞电压,-21V为定性离子对325.0/416.0的最优碰撞电压。
试验例6
基质效应考察:3种非法添加工业染料基质效应均<1,即3种非法添加工业染料均表现为基质抑制效应。综上,采用基质标准曲线法进行定量,详细数据见表3。
表3基质效应考察表
基质效应(%) | CR | MY | R2G |
肉制品 | 0.52 | 0.41 | 0.45 |
水产品 | 0.50 | 0.42 | 0.44 |
试验例7
方法学验证
线性关系与定量限:由于3种非法添加染料的响应不同,根据3倍信噪比计算检出限,10倍信噪比计算定量限,并建立相应的线性方程计算相关系数。得,刚果红、红2G的响应较低,酸性金黄的响应较高,酸性金黄的线性范围0.1~2.0μg/kg,刚果红、红2G的线性范围1.0~20.0μg/kg,相关系数均大于0.9944,当称样量为2.0g时,检出限为0.01~0.26μg/kg,定量限为0.02~0.88μg/kg,见表4。
表4 3种非法添加染料的线性方程、相关系数、线性范围、检出限、定量限数据
回收率和精密度:本试验采用肉制品进行标准添加实验,向空白肉制品中添加不同水平的目标物,其中刚果红、红2G添加水平为1#1.00μg/kg、2#5.00μg/kg、3#10.00μg/kg,酸性金黄添加水平为1#0.10μg/kg、2#0.5mg/kg、3#1.00mg/kg,3种非法添加染料的回收率在93.25~101.36%范围内,相对标准偏差RSD在1.27~4.06%范围内,见表5。
表5 3种非法添加剂染料在不同添加水平下的回收率和相对标准偏差
实际样品检测:
采用本方法对肉制品、水产品进行实际样品测试,特异性的低温共融物对于实际样品中的3种非法添加工业染料具有明显的特异吸附作用,可以应用于实际样品中3种非法添加工业染料的检测工作中,见图5。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种疏水性低温共融物的制备方法,其特征在于:包括如下步骤,将氢键受体和氢键供体混合,加热至混合物完全变成透明澄清液体,放凉至室温即得。
2.根据权利要求1所述的一种疏水性低温共融物的制备方法,其特征在于:所述氢键受体包括四丁基氯化铵、1-乙基-3-甲基咪唑氯盐、1-己基-3-甲基咪唑氯盐中的任一种。
3.根据权利要求1所述的一种疏水性低温共融物的制备方法,其特征在于:所述氢键供体包括正辛酸或正癸酸。
4.根据权利要求1所述的一种疏水性低温共融物的制备方法,其特征在于:氢键受体与氢键供体的摩尔比为1:1-1:3。
5.根据权利要求1所述的一种疏水性低温共融物的制备方法,其特征在于:50-60℃的油浴加热25-35分钟。
6.根据权利要求1所述的一种疏水性低温共融物的制备方法,其特征在于:55℃的油浴加热30分钟。
7.一种如权利要求1-6任一项所述的疏水性低温共融物的制备方法获得的疏水性低温共融物。
8.一种肉制品、水产品中三种非法添加工业染料的检测方法,其特征在于,包括如下步骤:
步骤1、取干燥的样品,加水超声,离心,取上清液;
步骤2、将疏水性低温共融物及所有上清液混合,涡旋,静置,产生油状液滴,吸取全部该油状液滴,用乙腈溶解并定容,微孔有机滤膜过滤,得滤液;
步骤3、滤液用液质联用仪测定。
9.根据权利要求8所述的一种肉制品、水产品中三种非法添加工业染料的检测方法,其特征在于,步骤1样品包括肉制品或水产品,肉制品取肌肉部分,水产品取皮和肉部分,均质干燥得干燥的样品;样品g与水mL的料液比为1:2-1:10,超声10min,10000rpm离心5min;步骤2中将50-400μL HDES及所有上清液置入10mL玻璃注射器中,涡旋1-3min,静置2min,产生油状液滴,吸取全部该油状液滴于2mL压盖离心管,用乙腈溶解并定容至1.0mL,过0.45μm微孔有机滤膜。
10.根据权利要求9所述的一种肉制品、水产品中三种非法添加工业染料的检测方法,其特征在于,步骤1样品g与水mL的料液比为1:5,超声10min,10000rpm离心5min;步骤2中将200μL HDES及所有上清液置入10mL玻璃注射器中,涡旋3min。
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Application publication date: 20200918 |