CN106084123A - 一种可裸眼检测镉离子浓度的反蛋白石凝胶光子晶体传感膜 - Google Patents
一种可裸眼检测镉离子浓度的反蛋白石凝胶光子晶体传感膜 Download PDFInfo
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Abstract
本发明公开了一种利用反蛋白石结构凝胶光子晶体传感膜,实现在水溶液中现场、实时检测Cd2+的方法。本发明首先制备了单分散聚苯乙烯微球,并组装成聚苯乙烯胶体晶体模板,继而以丙烯酰胺、烯丙基硫脲、过硫酸铵、N,N'‑亚甲基双丙烯酰胺组成前驱液填充在胶体晶体模板间隙,通过热聚合并脱除聚苯乙烯,得到反蛋白石凝胶光子晶体膜。在不同Cd2+浓度的溶液中,该凝胶光子晶体膜呈现不同的颜色,据此可以检测Cd2+。该方法还具有灵敏度高、选择性好和抗干扰性强,以及可以重复使用的特点。
Description
技术领域
本发明涉及一种可裸眼比色检测Cd2+浓度的反蛋白石凝胶光子晶体材料,属于光子晶体和分析检测技术领域。
背景技术
镉离子(Cd2+)进入人体后可能损伤人体功能器官,如造成人体骨骼萎缩、变形等。因此,Cd2+等重金属离子的检测成为现代检测技术领域的重要研究热点。目前,重金属离子的检测方法主要有原子吸收光谱,X射线荧光光谱,质谱法等,这些检测手段表现出了较高的灵敏度和准确度,但都需要复杂的仪器及繁琐的操作,甚至需要专业人员来进行检测。因此,建立一种快速、灵敏、方便的现场检测手段具有实际意义。
光子晶体是由不同折射率的介质材料在空间周期排列而形成的有序结构。其高度有序的结构可与一定波长的入射光发生相互作用发生Bragg衍射。光子晶体的晶格常数决定了其特征的Brag衍射峰波长,当入射光的波长落在可见光范围(400-800nm)时,光子晶体就会呈现出鲜艳的肉眼可见的结构颜色。天然存在的光子晶体的晶格常数是固定不变的,它的结构颜色不能随外界刺激发生变化。响应性水凝胶可以对外界物理或化学刺激响应而发生体积的可逆变化。将光子晶体与响应性水凝胶结合起来,利用凝胶的溶胀-收缩性质使光子晶体的晶格常数发生变化,引起光子晶体Bragg衍射峰位置的变化,从而使其结构颜色发生改变,即制得可对外界刺激响应的凝胶光子晶体。本发明采用“三明治”法制备了可与基底剥离的检测Cd2+的凝胶光子晶体传感膜,表现出了较好的响应性,很好的实现了Cd2+的快速比色检测。较其他检测手段而言,具备快速高效,操作简便,结果裸眼可视,灵敏性和抗干扰性强的优势。
发明内容
本发明的目的是解决水中镉离子常规检测方法的操作复杂繁琐,所需仪器昂贵,结果检测周期长等特点,公开一种利用反蛋白石结构凝胶光子晶体传感膜,在水溶液中现场、实时检测Cd2+的方法。
为实现上述目的,本发明采用了如下技术方案:
1.一种可裸眼检测镉离子浓度的反蛋白石凝胶光子晶体传感膜,其特征在于,包括以下步骤:
(1)聚苯乙烯(PS)微球和胶体晶体模板的制备
以苯乙烯为主单体,丙烯酸为交联单体,过硫酸铵为引发剂,二次蒸馏水为溶剂,采用无皂乳液聚合法,制备出分散系数为0.005聚苯乙烯-丙烯酸微球乳液(以下简称为PS乳液),取出一定量配制成固含量1%的PS乳液,超声震荡分散均匀后备用。采用双基片垂直沉积的方法制备面心立方密堆积结构(即FCC结构)的PS胶体晶体模板。
(2)反蛋白石结构的聚丙烯酰胺/聚稀丙基硫脲(PAM/PATU)凝胶光子晶体传感膜的制备
将丙烯酰胺、烯丙基硫脲、过硫酸铵、N,N'-亚甲基双丙烯酰胺溶解于13mL去离子水中,使其混合均匀,然后通入N2 10min以除去溶液中的O2得到预聚液备用。将一块洁净的载玻片,放置在已制备好的PS胶体晶体模板表面,两侧用夹子固定,形成类似“三明治”结构。将此“三明治”结构的PS胶体晶体模板平放于桌面,然后在模板一端边缘处逐滴缓慢滴下预聚液。然后再将其静置于45℃烘箱热引发聚合反应。反应结束后将“三明治”结构浸于去离子水中,使得蛋白石结构的凝胶光子晶体膜自动脱落,再将其浸于甲苯中约48h除去PS胶体晶体模板,最后得到颜色鲜艳的PAM/PATU反蛋白石凝胶膜。将反蛋白石凝胶膜置于无水乙醇中10s,除去残留的甲苯,自然干燥备用。
(3)PAM/PATU凝胶光子晶体传感膜对Cd2+的测定
将制得的凝胶光子晶体传感膜置于不同浓度的Cd2+溶液中,用光纤光谱仪测定其相应的Bragg衍射峰波长,并裸眼观察其颜色变化。
进一步地,所述的功能单体是丙烯酰胺(AM)和烯丙基硫脲(ATU),所述的交联剂是N,N-亚甲基双丙烯酰胺(BIS);所述的引发剂是过硫酸铵(APS);
进一步地,所述的丙烯酰胺加入量是32.4mmol,烯丙基硫脲加入量是1.2mmol;所述的引发剂过硫酸铵加入量是0.48mmol;所述的N,N-亚甲基双丙烯酰胺加入量是1.2mmol;
进一步地,所述的Cd2+水溶液浓度是0.010mmol/L~10mmol/L。
本发明的有益效果如下:(1)本发明将烯丙基硫脲引入到凝胶光子晶体中,烯丙基硫脲中的S与Cd2+较强的络合作用使得传感膜在水溶液中检测时具备特异性与灵敏性。(2)本发明采用的前驱液填充方法使前驱液的填充更为方便容易实现且有效减少了胶体晶体模板在填充时的滑动,可制得多层次的三维多孔结构;(3)本发明以高度有序大孔结构的光子晶体为模板,通过对不同浓度的镉离子检测,反蛋白石凝胶光子晶体传感膜发生宏观颜色变化,实现了对Cd2+的快速裸眼检测。(4)本发明制备的反蛋白石凝胶光子晶体传感膜机械性和化学稳定性好,且具有良好的可重复使用性能。
附图说明
图1是实施例1制备的PS胶体晶体模板SEM图。
图2是实施例2制备的反蛋白石结构凝胶光子晶体传感膜SEM图。从照片中可以看出,该凝胶光子晶体膜内部具有三维有序大孔结构。
图3是实施例3中制备的反蛋白石结构凝胶光子晶体传感膜在不同浓度Cd2+溶液的反射光谱图。其反射波长随溶液浓度增加发生蓝移,蓝移量为56nm。
具体实施方式
下面结合具体实施方式对本发明作进一步的详细描述,但这些实施例并不限制本发明的保护范围。
实施例1:聚苯乙烯微球和胶体晶体模板的制备
以苯乙烯为主单体,丙烯酸为交联单体,过硫酸铵为引发剂,二次蒸馏水为溶剂,采用无皂乳液聚合法,制备出分散系数为0.005聚苯乙烯-丙烯酸微球乳液(以下简称为PS乳液),取出一定量配制成固含量1%的PS乳液,超声震荡分散均匀后备用。在25mL烧杯中加入20mL质量分数为1%的PS微球乳液,然后将两块亲水处理后的载玻片垂直插入烧杯中,将烧杯置于温度为60℃,湿度为40%的恒温恒湿箱,待水分完全蒸发即可得到具有单一颜色的PS胶体晶体模板。
实施例2:反蛋白石结构的PAM/PATU凝胶光子晶体传感膜的制备
将AM(32.4mmol)、ATU(1.2mmol)、APS(0.48mmol)、BIS(1.3mmol)溶解于13mL去离子水中,使其混合均匀,然后通入N2 10min以除去溶液中的O2得到预聚液备用。将一块洁净的载玻片,放置在已制备好的PS胶体晶体模板表面,两侧用夹子固定,形成类似“三明治”结构。将此“三明治”结构的PS胶体晶体模板平放于桌面,然后在模板一端边缘处逐滴缓慢滴下预聚液,预聚液借助“三明治”结构形成的毛细作用力缓慢渗入胶体晶体的空隙中,当PS胶体晶体模板变为透明状态时,表明预聚液填充完毕。然后再将其静置于45℃烘箱热引发聚合反应。反应结束后将“三明治”结构浸于去离子水中,使得蛋白石结构的凝胶光子晶体膜自动脱落,再将其浸于甲苯中约48h除去PS胶体晶体模板,最后得到颜色鲜艳的PAM/PATU反蛋白石凝胶膜。将反蛋白石凝胶膜置于无水乙醇中10s,除去残留的甲苯,自然干燥备用。
实施例3:PAM/PATU凝胶光子晶体传感膜对浓度为0mmol/L,2.5mmol/L,10mmol/L的Cd2+溶液光谱检测
将制得的凝胶光子晶体传感膜置于不同浓度(0mmol/L,0.625mmol/L,1.25mmol/L,2.5mmol/L,5mmol/L,10mmol/L)的Cd2+溶液中,用光纤光谱仪测定其相应的Bragg衍射峰波长。当衍射峰波长的变化不超过3nm时,则认为传感膜对Cd2+的测定达到平衡。将完全响应的传感膜浸泡于洗脱液(0.8mol/L硫脲-3mol/L HCl)中10min,然后用去离子水冲洗干净,进行重复实验,并用数码相机拍摄相应的光学照片。
Claims (4)
1.一种可裸眼检测镉离子浓度的反蛋白石凝胶光子晶体传感膜,其特征在于,包括以下步骤:
(1)聚苯乙烯(PS)微球和胶体晶体模板的制备
以苯乙烯为主单体,丙烯酸为交联单体,过硫酸铵为引发剂,二次蒸馏水为溶剂,采用无皂乳液聚合法,制备出分散系数为0.005聚苯乙烯-丙烯酸微球乳液(以下简称为PS乳液),取出一定量配制成固含量1%的PS乳液,超声震荡分散均匀后备用;采用双基片垂直沉积的方法制备面心立方密堆积结构(即FCC结构)的PS胶体晶体模板;
(2)反蛋白石结构的聚丙烯酰胺/聚稀丙基硫脲(PAM/PATU)凝胶光子晶体传感膜的制备
将丙烯酰胺、烯丙基硫脲、过硫酸铵、N,N'-亚甲基双丙烯酰胺溶解于13mL去离子水中,使其混合均匀,然后通入N2 10min以除去溶液中的O2得到预聚液备用;将一块洁净的载玻片,放置在已制备好的PS胶体晶体模板表面,两侧用夹子固定,形成类似“三明治”结构;将此“三明治”结构的PS胶体晶体模板平放于桌面,然后在模板一端边缘处逐滴缓慢滴下预聚液;然后再将其静置于45℃烘箱热引发聚合反应;反应结束后将“三明治”结构浸于去离子水中,使得蛋白石结构的凝胶光子晶体膜自动脱落,再将其浸于甲苯中约48h除去PS胶体晶体模板,最后得到颜色鲜艳的PAM/PATU反蛋白石凝胶膜;将反蛋白石凝胶膜置于无水乙醇中10s,除去残留的甲苯,自然干燥备用;
(3)PAM/PATU凝胶光子晶体传感膜对Cd2+的测定
将制得的凝胶光子晶体传感膜置于不同浓度的Cd2+溶液中,用光纤光谱仪测定其相应的Bragg衍射峰波长,并裸眼观察其颜色变化。
2.根据权利要求1所述的一种可裸眼检测镉离子浓度的反蛋白石凝胶光子晶体传感膜,其特征在于,所述的功能单体是丙烯酰胺(AM)和烯丙基硫脲(ATU),所述的交联剂是N,N-亚甲基双丙烯酰胺(BIS),所述的引发剂是过硫酸铵(APS)。
3.根据权利要求1所述的一种可裸眼检测镉离子浓度的反蛋白石凝胶光子晶体传感膜,其特征在于,所述的丙烯酰胺加入量是32.4mmol,烯丙基硫脲加入量是1.2mmol,所述的引发剂过硫酸铵加入量是0.48mmol,所述的N,N-亚甲基双丙烯酰胺加入量是1.2mmol。
4.根据权利要求1所述的一种可裸眼检测镉离子浓度的反蛋白石凝胶光子晶体传感膜,其特征在于,所述的Cd2+水溶液浓度是0.010mmol/L~10mmol/L。
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CN112964672A (zh) * | 2021-03-18 | 2021-06-15 | 天津大学 | 一种检测磺胺甲噁唑的分子印迹光子晶体的制备方法及其应用 |
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CN113801270A (zh) * | 2021-08-12 | 2021-12-17 | 广州大学 | 一种凝胶材料及其制备方法和应用 |
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CN115228448A (zh) * | 2021-04-22 | 2022-10-25 | 湖南大学 | 一种壳聚糖基高分子聚合物吸附剂的制备及应用 |
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CN112778465A (zh) * | 2020-12-31 | 2021-05-11 | 苏州国纳思新材料科技有限公司 | 一种可逆变色的光子晶体水凝胶膜的制备方法 |
CN113008835A (zh) * | 2021-02-25 | 2021-06-22 | 陕西科技大学 | 一种光子晶体传感器及其制备方法和应用 |
CN112964672A (zh) * | 2021-03-18 | 2021-06-15 | 天津大学 | 一种检测磺胺甲噁唑的分子印迹光子晶体的制备方法及其应用 |
CN115228448A (zh) * | 2021-04-22 | 2022-10-25 | 湖南大学 | 一种壳聚糖基高分子聚合物吸附剂的制备及应用 |
CN113801270A (zh) * | 2021-08-12 | 2021-12-17 | 广州大学 | 一种凝胶材料及其制备方法和应用 |
CN114573860A (zh) * | 2022-02-23 | 2022-06-03 | 无锡职业技术学院 | 一种高度有序无裂纹反蛋白石结构分子印迹膜、制备方法及应用 |
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