CN108822253A - 2-甲氧基苯胺富集试剂的制备方法及其产品与应用 - Google Patents
2-甲氧基苯胺富集试剂的制备方法及其产品与应用 Download PDFInfo
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Abstract
本发明属于烟草检测技术领域,尤其涉及一种2‑甲氧基苯胺富集试剂的制备方法,还涉及由该制备方法制得的2‑甲氧基苯胺富集试剂,以及该2‑甲氧基苯胺富集试剂的应用。该制备方法操作简单,成本较低,适用于大规模工业化生产;该2‑甲氧基苯胺富集试剂能够特异性地吸附2‑甲氧基苯胺,而不会吸附其同分异构体或分子结构差异巨大的其它化合物;并且,该2‑甲氧基苯胺富集试剂在应用于吸附烟丝里的2‑甲氧基苯胺后,相关检测人员可另外建立2‑甲氧基苯胺的浓度‑紫外吸光度标准曲线,进一步利用紫外分光光度法测得烟丝中的2‑甲氧基苯胺的含量;该2‑甲氧基苯胺富集试剂完成吸附的时间短,适用于烟草品控的快速检测,因此具有广阔的应用前景。
Description
技术领域
本发明属于烟草检测技术领域,尤其涉及一种2-甲氧基苯胺富集试剂的制备方法,还涉及由该制备方法制得的2-甲氧基苯胺富集试剂,以及所述2-甲氧基苯胺富集试剂的应用。
背景技术
吸烟是一种不健康的生活习惯,烟草危害已成为当今世界严重的公共卫生问题之一。众所周知,卷烟点燃之后所产生的烟草烟雾中含有至少69种已知的致癌物;其中,主要的有害化学物质包括5大类:(1)醛类、氮化物,这些物质对呼吸道有刺激作用;(2)尼古丁,可刺激交感神经,让吸烟者形成依赖;(3)胺类、氰化物和重金属,这些均属于毒性物质;(4)苯并芘、砷、其它放射性物质,这些物质均有致癌作用;(5)一氧化碳,能大大减低红细胞将氧输送到全身的能力。
其中,结构式如下所示的2-甲氧基苯胺易被人体吸收:
特别是,2-甲氧基苯胺毒性较高,明显刺激皮肤和黏膜,容易引起过敏症。2-甲氧基苯胺在空气中最高容许浓度为0.5mg/m3;其急性毒性至少包括:
口腔LD50 1400mg/kg(mus)
1150mg/kg(rat)
870mg/kg(rbt)。
并且,2-甲氧基苯胺的主要刺激性影响包括:在皮肤上面:对皮肤有一定刺激作用;若进入眼睛则可引起发炎。
然而,目前有关卷烟侧流烟气中有害化合物分析主要是采用气相色谱(GC)法、气质联用(GC/MS)法以及液质联用(LC/MS)法。但是这些检测方法都需要大型的仪器设备,这些设备的使用和日常维护费用较高,因此需要很高的检测成本。除此之外,气相检测受试样的挥发性和热稳定性限制,应用范围窄,流动相种类较少;液相的检测时间较长。因此选择成本更低,操作简单的检测方法是很有必要的。
分子印迹技术(Molecular Imprinting Technology,MIT)是指制备对某一特定的目标分子(又称为模板分子或印迹分子)具有选择性的聚合物的技术。在1894年,在解释酶作用的专一性的时候,E.Fischer就提出了“锁与钥匙”的学说,即酶和底物结合时,底物的结构和酶的活动中心的结构十分吻合,酶的这种互补形状,使酶只能与对应的化合物对应,从而排斥了那些形状、大小不适合的化合物。人们根据酶与底物分子的专一性结合特性,在1949年,Dickey首次提出了“分子印迹”的概念;他以甲基橙作为模板分子,以酸化的硅酸盐作为单体,引发聚合之后,用甲醇作为洗脱液洗脱甲基橙,制得了甲基橙分子的印迹硅胶。这种材料和空白的硅胶相比,对于甲基橙的吸附作用明显增大。到1972年,德国的Wulff研究小组首次报道了人工合成的分子印迹聚合物后,这项技术才逐渐被人们所认识。特别是在1993年,瑞典科学家Mosbach等在《Nature》杂志上发表了有关茶碱分子印迹聚合物的研究报告,阐述了分子印迹的“塑料抗体”和仿生免疫分析的应用,使分子印迹技术得到全世界的瞩目,分子印迹技术才得到了蓬勃的发展。
分子印迹技术之所以能够发展如此迅速,主要是因为有三大优点:预定性:模板分子和功能单体在聚合之前是已经选择好了的,所以这种预定性就决定了人们可以按照自己的目的制备不同的分子印迹聚合物(NIP),以满足各种不同的需要;特异性识别:NIP是按照模板分子的构型聚合的,因此它具特异的识别位点和空腔来识别模板分子,因而其特异性识别作用很强;实用性:NIP的稳定性好,通常不受高温、酸碱的影响。分子印迹聚合物同天然生物分子,如酶和底物、抗原和抗体、受体和激素相比能够抵御比较恶劣的环境影响,而且贮存条件温和,能够长时间保留识别性能。特别是,制备得到的纳米级的分子印迹聚合物表面有模板分子的“印迹腔”,当分子印迹聚合物应用到模板分子存在的体系中后,该分子印迹聚合物就能选择性吸附目标分子(模板分子),从而将目标分子与其他物质分离。
发明内容
针对现有烟草检测技术中对2-甲氧基苯胺单一成分专属分析方法的不足,本发明旨在提供一种富集试剂,用于特异性地吸附2-甲氧基苯胺,而不会吸附其同分异构体或分子结构差异巨大的其它化合物;进一步地,该富集试剂能够被用于吸附烟丝里微量存在的2-甲氧基苯胺,从而有利于实施烟草质量检测。
因此,本发明第一方面提供了一种2-甲氧基苯胺富集试剂的制备方法,其包括以下步骤:
S1:准确称取丙烯酸、单体α、交联剂β,超声溶于水中;然后加入单体γ的无水乙醇溶液,超声脱气;
S2:调节pH=6~7后,加入作为模板分子的2-甲氧基苯胺;
S3:缓慢地滴加引发剂的水溶液,在32~35℃下聚合反应20~25h;
S4:反应完全后,以乙醇-氯仿为萃取剂,采用索氏提取器进行回流过夜,以洗脱模板分子,制得分子印迹聚合物粗品;
S5:将所述分子印迹聚合物粗品进行透析以去除未聚合的引发剂或/和丙烯酸或/和单体α或/和单体γ,然后冻干透析液,制得分子印迹聚合物固体粉末,即为2-甲氧基苯胺富集试剂;
其中,所述单体α的结构式为:
其中,所述交联剂β的结构式为:
其中,所述单体γ的结构式为:
优选地,在上述制备方法中,在S1中,所述丙烯酸与所述单体α的摩尔比为1:2,所述丙烯酸与所述交联剂β的摩尔比为1:10,所述丙烯酸与所述单体γ的摩尔比为1:1。
优选地,在上述制备方法中,在S1中,所述超声脱气的持续时间为5~15min。
优选地,在上述制备方法中,所述丙烯酸与所述2-甲氧基苯胺的摩尔比为1:2~1:16。
进一步优选地,在上述制备方法中,所述丙烯酸与所述2-甲氧基苯胺的摩尔比为1:8。
优选地,在上述制备方法中,所述引发剂由过硫酸铵、亚硫酸氢钠和十二烷基硫酸钠组成。
另外,值得补充说明的是,在本文中,各步骤所使用的水均为蒸馏水。
本发明第二方面提供了一种2-甲氧基苯胺富集试剂,其由本发明第一方面所述的制备方法制得。
同时,本发明第三方面提供了第二方面所述的2-甲氧基苯胺富集试剂在特异性吸附烟丝里的2-甲氧基苯胺中的应用,包括以下步骤:
取所述2-甲氧基苯胺富集试剂,超声溶于水中,配制成富集试剂溶液;然后,将烟丝的乙醇溶液与所述富集试剂溶液混合,超声振荡20~30min,完成特异性吸附。
优选地,在上述应用中,所述富集试剂溶液的浓度为1mg/mL。
优选地,在上述应用中,所述烟丝的乙醇溶液的制备步骤包括:
称取卷烟烟丝,置于无水乙醇中,水浴加热回流0.5~1.5小时,接着,先抽滤,再用220nm微孔滤膜过滤,即得所述烟丝的乙醇溶液。
与现有技术相比,本发明所提供的技术方案具备以下有益效果:本发明所提供的2-甲氧基苯胺富集试剂的制备方法操作简单,成本较低,适用于大规模工业化生产;本发明所提供的2-甲氧基苯胺富集试剂,实际上是一种分子印迹聚合物,其能够特异性地吸附2-甲氧基苯胺,而不会吸附其同分异构体或分子结构差异巨大的其它化合物;此外,所述2-甲氧基苯胺富集试剂在应用于吸附烟丝里的2-甲氧基苯胺后,相关检测人员可另外建立2-甲氧基苯胺的浓度-紫外吸光度标准曲线,进一步利用紫外分光光度法测得烟丝中的2-甲氧基苯胺的含量;并且,所述2-甲氧基苯胺富集试剂完成吸附的时间短,适用于烟草品控的快速检测,因此具有广阔的应用前景。
附图说明
图1为分子印迹聚合物的制备原理示意图;
图2为本发明所述的2-甲氧基苯胺富集试剂的TEM图;
图3(A)为2-甲氧基苯胺的浓度-紫外吸光度标准曲线,图3(B)为2-甲氧基苯胺富集试剂吸附前后的2-甲氧基苯胺(5μg/mL)的紫外吸收图。
具体实施方式
下面结合具体实施方式对本发明作进一步阐述,但本发明并不限于以下实施方式。下述实施例中的实验步骤,如无特殊说明,均为常规操作;下述实施例中所使用的材料、试剂等,如无特殊说明,均可从公开商业途径获得。
根据本发明的第一方面,在一个优选实施例中,2-甲氧基苯胺富集试剂的制备方法包括以下步骤:
S1:准确称取丙烯酸(0.2-0.3mmol)、单体α、交联剂β,超声溶于80mL水中;然后加入单体γ的无水乙醇(1mL)溶液,超声脱气10min;
S2:调节pH=6~7后,加入作为模板分子的2-甲氧基苯胺;
其中,分别按以下摩尔比投加模板分子:
NIP-1:(丙烯酸:模板分子=1:2)
NIP-2:(丙烯酸:模板分子=1:4)
NIP-3:(丙烯酸:模板分子=1:8)
NIP-4:(丙烯酸:模板分子=1:16)
S3:缓慢地滴加引发剂(过硫酸铵,亚硫酸氢钠和十二烷基硫酸钠)的水溶液,在32~35℃下聚合反应20~25h;
S4:反应完全后,以乙醇-氯仿为萃取剂,采用索氏提取器进行回流过夜,以洗脱模板分子,制得分子印迹聚合物粗品;
S5:将所述分子印迹聚合物粗品用蒸馏水透析2~3天,每天换水3次,以去除未聚合的引发剂或/和丙烯酸或/和单体α或/和单体γ,然后冻干透析液,制得分子印迹聚合物固体粉末,即为2-甲氧基苯胺富集试剂;
其中,所述单体α的结构式为:
其中,所述交联剂β的结构式为:
其中,所述单体γ的结构式为:
根据本发明第二方面的2-甲氧基苯胺富集试剂,其由第一方面所述的制备方法制得。
根据本发明第三方面的2-甲氧基苯胺富集试剂在特异性吸附烟丝里的2-甲氧基苯胺中的应用,包括以下步骤:
取所述2-甲氧基苯胺富集试剂,超声溶于水中,配制成富集试剂溶液;其中,所述富集试剂溶液的浓度为1mg/mL;然后,称取5g卷烟烟丝,置于250ml无水乙醇中,水浴加热回流0.5小时,接着,先抽滤,取粗滤液,再将该粗滤液用220nm微孔滤膜过滤,取滤液,即得烟丝的乙醇溶液;将所述烟丝的乙醇溶液与所述富集试剂溶液混合,超声振荡20~30min,完成特异性吸附;
此外,用HPLC的方法检测各个2-甲氧基苯胺富集试剂对2-甲氧基苯胺的吸附能力,确定吸附量最大的富集试剂,结果富集试剂NIP-3的吸附量最大。
实施例1:
准确称取丙烯酸(0.2mmol),单体α(0.4mmol),交联剂β(2mmol)超声溶于80mL蒸馏水,并加入单体γ(0.2mmol)的1mL无水乙醇溶液,超声脱气10min;然后,用NaOH调节pH=7,加入1.6mmol模板分子(2-甲氧基苯胺)(其溶于蒸馏水),70rpm恒温(35℃)振荡4小时;接着,以1~2滴/秒的速度缓慢地滴加引发剂的水溶液(过硫酸铵(60.0mg),亚硫酸氢钠(20.0mg),十二烷基硫酸钠(40.0mg)溶于20mL的蒸馏水),在35℃下聚合反应21h;
反应完全后,以乙醇-氯仿为萃取剂,采用索氏提取器回流过夜,以洗脱模板分子(2-甲氧基苯胺),制得分子印迹聚合物粗品;
将所述分子印迹聚合物粗品用蒸馏水透析2~3天,每天换水3次,以去除未聚合的引发剂或/和丙烯酸或/和单体α或/和单体γ,然后冻干透析液,制得2-甲氧基苯胺富集试剂NIP-3,如图2所示,其为粒径约200nm的纳米球;
取所述2-甲氧基苯胺富集试剂NIP-3,超声溶于水中,配制成1mg/mL富集试剂溶液;
称取5g卷烟烟丝,置于250ml无水乙醇中,水浴加热回流1.5小时,接着,先抽滤,取粗滤液,再将该粗滤液用220nm微孔滤膜过滤,取滤液,即得烟丝的乙醇溶液;将该烟丝的乙醇溶液与所述富集试剂溶液混合,超声振荡30min,完成选择性吸附。
实施例2:
①配制富集试剂溶液(1mg/mL)
准确称取5.0mg 2-甲氧基苯胺富集试剂NIP-3超声溶于5.0mL的蒸馏水中,配制成1mg/mL的富集试剂溶液;
②2-甲氧基苯胺的浓度-紫外吸光度标准曲线的测定(0.1,0.2,0.5,1.0,2.0,4.0,5.0,10.0μg/mL)
购买或自行配制100μg/mL的2-甲氧基苯胺的标准溶液:准确称取2.0mg 2-甲氧基苯胺,溶于20.0mL的无水乙醇。
10μg/ml 2-甲氧基苯胺溶液的配制:1ml 100μg/ml 2-甲氧基苯胺溶液+9ml无水乙醇;5μg/ml 2-甲氧基苯胺溶液的配制:5ml 10μg/ml 2-甲氧基苯胺溶液+5ml无水乙醇;4μg/ml 2-甲氧基苯胺溶液的配制:2ml 10μg/ml 2-甲氧基苯胺溶液+3ml无水乙醇;2μg/ml2-甲氧基苯胺溶液的配制:2ml 5μg/ml 2-甲氧基苯胺溶液+3ml无水乙醇;1μg/ml 2-甲氧基苯胺溶液的配制:3ml 5μg/ml2-甲氧基苯胺溶液+12ml无水乙醇;0.5μg/ml 2-甲氧基苯胺溶液的配制:6ml 1μg/ml2-甲氧基苯胺溶液+6ml无水乙醇;0.2μg/ml 2-甲氧基苯胺溶液的配制:4ml0.5μg/ml2-甲氧基苯胺溶液+6ml无水乙醇;0.1μg/ml 2-甲氧基苯胺溶液的配制:4ml 0.2μg/ml 2-甲氧基苯胺溶液+4ml无水乙醇;检测各浓度下的紫外吸光度,制作标准曲线,如图3(A)所示。
③快速吸附2-甲氧基苯胺
室温条件下,取2.0mL的富集试剂溶液,并取1.0mL 2-甲氧基苯胺溶液(5μg/ml),置于5ml的离心管中,超声振荡20min,离心(10000rpm/30min)后,取上清液。
④紫外分光光度计检测富集试剂的吸附量,计算Q值(参见图3(B)):
2-甲氧基苯胺溶液(5μg/mL)的紫外吸光度为1.013(283nm);经过2-甲氧基苯胺富集试剂NIP-3吸附并离心后,上清液中的2-甲氧基苯胺的紫外吸光度为0.245(283nm),根据标准曲线计算得到该上清液中的2-甲氧基苯胺的浓度为Ct=1.5μg/mL。
根据公式Q=[(C0-Ct)×V]/M计算Q值;其中C0—吸附前2-甲氧基苯胺的浓度(mg/mL),Ct—吸附并离心后的上清液中的2-甲氧基苯胺的浓度(mg/mL),V—加入的2-甲氧基苯胺溶液的体积(mL),M—加入的富集试剂质量(g);计算结果为Q=1.75mg/g,即说明每克2-甲氧基苯胺富集试剂NIP-3能够选择性地吸附1.75mg 2-甲氧基苯胺。
实施例3:
取市售的一种卷烟Y,切开后,将烟丝取出烘干,按照实施例1中所述的步骤制得烟丝的乙醇溶液,将该烟丝的乙醇溶液与实施例2中配制的富集试剂溶液(1mg/mL)混合,超声振荡25min,完成选择性吸附;进一步以乙醇-氯仿为萃取剂,采用索氏提取器回流过夜,以洗脱2-甲氧基苯胺,然后在建立了2-甲氧基苯胺的浓度-紫外吸光度标准曲线的基础上,利用紫外分光光度法测得萃取剂中的2-甲氧基苯胺的含量,从而间接测得了卷烟Y的烟丝中的2-甲氧基苯胺的含量。并且,由于紫外分光光度法是本领域内所已知的技术,因此,在本文中不再赘述。
以上对本发明的具体实施例进行了详细描述,但其只是作为范例,本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言,任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此,在不脱离本发明的精神和范围下所作的均等变换和修改,都应涵盖在本发明的范围内。
Claims (10)
1.一种2-甲氧基苯胺富集试剂的制备方法,其特征在于,包括以下步骤:
S1:准确称取丙烯酸、单体α、交联剂β,超声溶于水中;然后加入单体γ的无水乙醇溶液,超声脱气;
S2:调节pH=6~7后,加入作为模板分子的2-甲氧基苯胺;
S3:缓慢地滴加引发剂的水溶液,在32~35℃下聚合反应20~25h;
S4:反应完全后,以乙醇-氯仿为萃取剂,采用索氏提取器进行回流过夜,以洗脱模板分子,制得分子印迹聚合物粗品;
S5:将所述分子印迹聚合物粗品进行透析以去除未聚合的引发剂或/和丙烯酸或/和单体α或/和单体γ,然后冻干透析液,制得分子印迹聚合物固体粉末,即为2-甲氧基苯胺富集试剂;
其中,所述单体α的结构式为:
其中,所述交联剂β的结构式为:
其中,所述单体γ的结构式为:
2.根据权利要求1所述的2-甲氧基苯胺富集试剂的制备方法,其特征在于,在S1中,所述丙烯酸与所述单体α的摩尔比为1:2,所述丙烯酸与所述交联剂β的摩尔比为1:10,所述丙烯酸与所述单体γ的摩尔比为1:1。
3.根据权利要求1所述的2-甲氧基苯胺富集试剂的制备方法,其特征在于,在S1中,所述超声脱气的持续时间为5~15min。
4.根据权利要求1所述的2-甲氧基苯胺富集试剂的制备方法,其特征在于,所述丙烯酸与所述2-甲氧基苯胺的摩尔比为1:2~1:16。
5.根据权利要求4所述的2-甲氧基苯胺富集试剂的制备方法,其特征在于,所述丙烯酸与所述2-甲氧基苯胺的摩尔比为1:8。
6.根据权利要求1所述的2-甲氧基苯胺富集试剂的制备方法,其特征在于,所述引发剂由过硫酸铵、亚硫酸氢钠和十二烷基硫酸钠组成。
7.一种2-甲氧基苯胺富集试剂,其特征在于,所述2-甲氧基苯胺富集试剂由根据权利要求1~6中任一项所述的制备方法制得。
8.根据权利要求7所述的2-甲氧基苯胺富集试剂在特异性吸附烟丝里的2-甲氧基苯胺中的应用,其特征在于,包括以下步骤:
取所述2-甲氧基苯胺富集试剂,超声溶于水中,配制成富集试剂溶液;然后,将烟丝的乙醇溶液与所述富集试剂溶液混合,超声振荡20~30min,完成特异性吸附。
9.根据权利要求8所述的应用,其特征在于,所述富集试剂溶液的浓度为1mg/mL。
10.根据权利要求8所述的应用,其特征在于,所述烟丝的乙醇溶液的制备步骤包括:
称取卷烟烟丝,置于无水乙醇中,水浴加热回流0.5~1.5小时,接着,先抽滤,再用220nm微孔滤膜过滤,即得所述烟丝的乙醇溶液。
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