CN110903467A - 侧基含有罗丹明b单元的荧光共轭高分子、制备方法及其应用 - Google Patents

侧基含有罗丹明b单元的荧光共轭高分子、制备方法及其应用 Download PDF

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CN110903467A
CN110903467A CN201910934972.0A CN201910934972A CN110903467A CN 110903467 A CN110903467 A CN 110903467A CN 201910934972 A CN201910934972 A CN 201910934972A CN 110903467 A CN110903467 A CN 110903467A
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范丽娟
张毅晨
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Abstract

本发明涉及一种侧基含有罗丹明B单元的荧光共轭高分子、制备方法及其应用。将含有罗丹明B单元的单体和双癸基2,2'‑（（2,5‑二乙炔基‑1,4‑亚苯基）双（氧））二乙酸酯单体通过Sonogashira偶联，得到一种侧基含有罗丹明B单元的荧光共轭高分子聚合物。本发明提供的聚合物，它的四氢呋喃溶液在激发波长分别为360nm和520nm的条件下，可用于水中铁离子（Fe3+）以及亚铁离子（Fe2+）的选择性检测，具有良好的抗干扰能力。检测时，采用双激发的方式，将两处最大发射波长处的荧光强度比值作为结果输出，可有效降低环境因素引起的误差，提高检测精确。

Description

侧基含有罗丹明B单元的荧光共轭高分子、制备方法及其应用
技术领域
本发明涉及一种侧基含有罗丹明B单元的荧光共轭高分子的合成及其对于水溶液中的铁离子（Fe3+）和亚铁离子(Fe2+)的的传感检测，属于荧光传感材料技术领域。
背景技术
由于共轭高分子存在的分子导线效应，因此，具有放大荧光信号的作用，并且其结构易于调控，可以通过引入适当的官能团，实现对某一类物质的特异性响应。罗丹明系列染料由于其荧光量子产率高、光稳定性好、价廉易得等优点，已被广泛用作各类离子或分子探针（参见文献：Chem. Soc. Rev., 2008, 37, 1465—1472；Chem. Rev.2012, 112, 1910—1956）；也有文献报道了含有罗丹明染料的共轭高分子应用于金属离子的溶液检测（参见文献：Macromol. Rapid Commun. 2009, 30, 1339—1344；Chem. Commun., 2014, 50,2040—2042；RSC Adv., 2017, 7, 39852—39858）。上述公开的金属离子探针，一部分是基于单一发射波长处的荧光强度变化的探针，这类探针容易受到环境因素(如温度、湿度、pH值等)的干扰，而使结果不够精确；另一部分是基于两种发射波长处的荧光强度比值变化的比率式荧光探针，这类探针相比基于单一发射波长处荧光强度变化的探针，有着更优秀的抗干扰性。但此类探针多是单一激发，主要是利用了能量转移机理，因此，其结果存在着无法避免氢离子(H+)造成的干扰的不足。
发明内容
本发明针对现有技术存在的不足，提供一种侧链带有罗丹明B单元的荧光共轭高分子及其制备方法，用于对铁离子（Fe3+）和亚铁离子（Fe2+）进行双激发比率式检测，具有良好的抗干扰能力，能有效提高检测精度。
实现本发明目的的技术方案是提供一种侧基含有罗丹明B单元的荧光共轭高分子，它的结构式为：
Figure 100002_DEST_PATH_IMAGE002
，
其中，n为聚合度，n=15~50。
本发明技术方案还提供一种侧基含有罗丹明B单元的荧光共轭高分子的制备方法，按物质的量计，将1份单体M1和1份单体M2，0.015~0.05份四（三苯基膦）钯，0.015~0.05份碘化亚铜，30~60份二异丙胺，100~200份甲苯混合搅拌，在氩气保护，温度为65℃~75℃的条件下反应；反应结束后,再经纯化、干燥，得到一种侧基含有罗丹明B单元的荧光共轭高分子；
所述单体M1的结构式为：
Figure 100002_DEST_PATH_IMAGE004
；
单体M2的结构式为：
Figure 100002_DEST_PATH_IMAGE006
。
本发明提供的侧基含有罗丹明B单元的荧光共轭高分子的应用，将它溶解于四氢呋喃溶剂中，按重复单元计, 溶液浓度为1×10-5 M~5×10-4 M；在激发波长分别为360nm和520nm的条件下，用于对水中的铁离子Fe3+和亚铁离子Fe2+进行选择性双激发比率式检测。
本发明提供的荧光共轭高分子聚合物，其应用于双激发比率式检测的原理是：由于其侧链含有的罗丹明B螺内酰胺，在闭环的状态下其无荧光发射，但是，当在铁离子（Fe3+）或亚铁离子（Fe2+）存在的条件下，闭环的螺内酰胺将与离子配位而开环，发射荧光；还由于铁离子（Fe3+）亚铁离子（Fe2+）在四氢呋喃溶液中，对波长为365nm存在吸收，因此，当用360nm的激发光激发时，它们可以淬灭聚合物主链的荧光（内滤效应）；同时,氢离子（H+）也会使罗丹明B螺内酰胺开环，但它不会淬灭聚合物主链的荧光（无内滤效应），因此，利用铁离子和亚铁离子可淬灭聚合物骨架荧光和诱导罗丹明B螺内酰胺，从而产生荧光发射的能力，可运用双激发的方式进行比率式检测。
与现有技术相比，本发明的有益效果在于：.
1.本发明合成了一种侧基带有罗丹明B单元的共轭高分子，可用于水中铁离子（Fe3+）和亚铁离子（Fe2+）的双激发比率式检测，具有良好的抗干扰性和检测限，且能对氢离子（H+）加以鉴别，提高了检测精度。
2.本发明无需借助复杂的仪器，仅需要荧光仪器即可进行定性或定量检测，操作方便。
附图说明
图1是本发明提供的一种侧基含有罗丹明B单元的荧光共轭高分子PPETE-RB的合成路线示意图；
图2是本发明实施例制备的两种单体原料和荧光共轭高分子PPETE-RB的核磁谱图；
图3是本发明实施例制备的两种单体原料和荧光共轭高分子PPETE-RB的红外谱图；
图4是本发明实施例制备的荧光共轭高分子PPETE-RB在不同溶剂中的吸收和发射谱图；
图5是本发明实施例制备的荧光共轭高分子PPETE-RB的四氢呋喃溶液的选择性检测图；
图6是本发明实施例制备的荧光共轭高分子PPETE-RB的四氢呋喃溶液检测的抗干扰能力图；
图7是本发明实施例制备的荧光共轭高分子PPETE-RB的四氢呋喃溶液对于不同浓度的铁离子和亚铁离子的检测结果图；
图8是本发明实施例制备的荧光共轭高分子PPETE-RB的四氢呋喃溶液对于不同浓度的氢离子的响应图。
具体实施方式
下面结合附图和实施例对本发明技术方案作进一步的阐述。
实施例1
参见附图1，它是本实施例制备侧基含有罗丹明B单元的荧光共轭高分子PPETE-RB的合成路线示意图。
在本实施例中，单体M1的合成可参见文献(ACS Appl. Mater. Interfaces 2014,6, 5041-5049)。
M1的结构式为：
Figure 746670DEST_PATH_IMAGE004
；
M2的结构式为：
Figure DEST_PATH_IMAGE007
；
M2的合成可参见文献（Macromol. Rapid Commun. 2009, 30, 1339-1344, Org. Lett., 2007, 9, 3921-3924）,并作了条件的优化。单体M2的制备方法为：将化合物1(0.300 g, 0.075 mmol)、催化剂1-(3-二甲氨基苯基)-3-乙基碳二亚胺盐酸盐(EDCI)(0.075 mmol, 0.014 g)、1-羟基苯并三唑(HOBt) (0.075 mmol, 0.010 g)和三乙胺(Et3N)(0.1875 mmol, 0.019 g)依次加入到50 mL的双口烧瓶中，然后再加入二氯甲烷，在冰浴下搅拌1小时，然后再加入化合物2 (0.300 g, 0.075 mmol)，撤去冰浴，在室温下反应24小时。反应结束后，将反应物旋干，然后经过硅胶柱纯化，洗脱液中可加入少量三乙胺，将滤液旋干，干燥，得到黄色固体。产量：0.322g, 产率：52.10 %。1H NMR (400 MHz, CDCl3)δ 7.94 – 7.86 (m, 1H), 7.48 – 7.42 (m, 2H), 7.15 – 7.05 (m, 1H), 6.96 (s,1H), 6.90 (s, 1H), 6.40 (m, 4H), 6.27 (m, 2H), 4.96 (s, 2H), 3.33 (m, 10H),3.05 (m, 2H), 2.34 (m, 2H), 2.10 (m, 2H), 1.62 (d, 4H), 1.16 (t, 12H).Elemental Anal. Calcd for C41H46Br2N4O5S(%): C, 56.93; N, 6.48; H, 5.37;found: C, 55.52; N, 6.22; H, 5.79. QTOF-MS: Calcd for C41H46Br2N4O5S: m/z889.1433(M1+Na+); found: m/z 889.1409 (M1+Na+).
化合物1的结构式为：
Figure DEST_PATH_IMAGE009
，
化合物2的结构式为：
Figure DEST_PATH_IMAGE011
。
附图1中，聚合物PPETE-RB的制备：在氩气保护下，将单体M1(76 mg, 0.13 mmol)、单体M2（108 mg, 0.13 mmol）、催化剂四（三苯基膦）钯（12mg, 0.01 mmol）和碘化亚铜（2mg, 0.01 mmol）依次加入到50mL的双口烧瓶中，然后再加入重蒸的二异丙胺4 mL和甲苯10 mL, 升温至75℃，回流搅拌48h。反应结束后，冷却至室温，用0. 22 μm 的过滤头过滤反应液，取所得滤液旋干。然后再将旋干后的粗产物溶于尽量少的三氯甲烷（2~3 mL）再将滤液滴入至60 mL甲醇中沉淀得到产物。将产物放入真空干燥箱，得到棕黄色固体。产量：0.097g，产率：61.38%。1H NMR (400 MHz, CDCl3) δ 7.82 (m, 1H), 7.44 (m, 2H), 7.16(s, 1H), 7.09 – 7.05 (m, 1H), 7.05 – 7.00 (m, 1H), 6.90 (s, 2H), 6.40-6.27(m, 6H), 4.99 (s, 2H), 4.68 (s, 4H), 4.21 (m, 4H), 3.37 – 3.25 (m, 10H), 3.04(m, 2H), 2.36 (m, 2H), 2.10 (m, 2H), 1.64 (m, 8H), 1.25 (m, 36H), 1.16 (t,12H), 0.86 (t, 6H). Calcd for C79H102N4O5S (%): C, 71.94; N, 4.25; H, 7.95;found: C, 66.94; N, 4.09; H, 7.30. GPC:
Figure RE-RE-DEST_PATH_IMAGE013
=35.4 kDa;
Figure RE-RE-DEST_PATH_IMAGE015
=23.5 kDa; PDI=1.51,n=18; UV-vis λmax: 441 nm, Emission λmax: 484 nm. Φf = 28% in THF.
参见附图2，它是本实施例提供的单体M1和M2以及聚合物PPETE-RB的核磁谱图，由图2可以看出，制备的M1，M2，PPETE-RB与合成路线图中的所示结构一致。
参见附图3，它是本实施例提供的单体M1和M2以及聚合物PPETE-RB的红外谱图，由图3可进一步证实，M1，M2以及PPETE-RB与合成路线图中所示结构相同。
参见附图4，它是由本实施例制备的聚合物在不同溶剂中的归一化紫外吸收和荧光发射谱图。
实施例2
本实施例采用实施例1提供的共轭高分子聚合物PPETE-RB，用于检测水环境中的铁离子（Fe3+）和亚铁离子（Fe2+）。
将共轭高分子聚合物PPETE-RB溶解在THF溶液中，浓度为1×10-4 M (按重复单元计)。
将各金属离子(依次为Ba2+, Ca2+, Cd2+, Cr3+, Cu2+, Fe2+, Fe3+, Hg2+, K+, Na+,Pb2+)溶解在三（羟甲基）氨基甲烷-盐酸（Tris-HCl）缓冲溶液中，浓度为3mM，作为储存液待用。
取2.9 mL共轭高分子聚合物PPETE-RB的四氢呋喃溶液，滴加0.1 mL上述各金属离子的缓冲溶液，在振荡器上震荡90分钟，然后逐个进行荧光测试，荧光发射谱图上最大发射波长处的荧光强度变化即为响应，将571nm处的荧光发射强度与481nm出的荧光发射强度的比值作为结果输出。
在检测时，选择双激发的方式，具体操作如下：同一个样品，先用360nm的激发光激发（狭缝设置为Ex=3 nm, Em=1.5 nm）；然后再用520nm的激发光激发（狭缝设置为Ex=5 nm,Em=3 nm）。每组数据测试三遍。
参见附图5，它是本实施例按照上述方法测得的聚合物的四氢呋喃溶液对不同金属离子的响应。由图5可以看出聚合物溶液对于铁离子（Fe3+）/亚铁离子（Fe2+）有明显的响应，具体表现为在481nm处的荧光发射强度降低并在571nm处的荧光发射增强。
参见附图6，它是本实施按上述方法测得的聚合物的四氢呋喃溶液对于铁离子（Fe3+ A图）/亚铁离子（Fe2+ B图）的检测的抗干扰性测试。由图6可以看出，该聚合物的四氢呋喃溶液对于铁离子（Fe3+）（A图）/亚铁离子（Fe2+）（B图）的检测有一定的抗干扰性。
附图6中混合离子溶液指铁离子（Fe3+）/亚铁离子（Fe2+）和其他金属离子各1×10-4 M，单一离子是只含有单一金属离子，浓度为1×10-4 M。
参见附图7，它是本实施例聚合物四氢呋喃溶液对于不同浓度铁离子（Fe3+）（A图）/亚铁离子（Fe2+）（B图）的检测结果图。由图7可以看出，随着铁离子（Fe3+）/亚铁离子（Fe2+）浓度的升高，波长481nm处的荧光强度降低，而波长为571nm处的荧光强度增强。根据两处的荧光强度比（I571/I481），通过计算，得到聚合物四氢呋喃溶液对于铁离子（Fe3+）/亚铁离子（Fe2 +）的检测限分别为4.4×10-6M和4.9×10-6M。
参见附图8，它是本实施例按照上述方法测得的对于不同浓度氢离子（H+）的响应。由图8可以看出，随着氢离子（H+）浓度升高，波长481nm处的荧光强度不会淬灭，这点与聚合物溶液对铁离子（Fe3+）/亚铁离子的响应不同，因此可以加以区别。

Claims (3)

1.一种侧基含有罗丹明B单元的荧光共轭高分子，其特征在于它的结构式为：
Figure DEST_PATH_IMAGE002
，
其中，n为聚合度，n=15~50。
2.一种侧基含有罗丹明B单元的荧光共轭高分子的制备方法，其特征在于：按物质的量计，将1份单体M1和1份单体M2，0.015~0.05份四（三苯基膦）钯，0.015~0.05份碘化亚铜，30~60份二异丙胺，100~200份甲苯混合搅拌，在氩气保护，温度为65℃~75℃的条件下反应；反应结束后,再经纯化、干燥，得到一种侧基含有罗丹明B单元的荧光共轭高分子；
所述单体M1的结构式为：
Figure DEST_PATH_IMAGE004
；
单体M2的结构式为：
Figure DEST_PATH_IMAGE006
。
3.一种侧基含有罗丹明B单元的荧光共轭高分子的应用，其特征在于：将它溶解于四氢呋喃溶剂中，按重复单元计, 溶液浓度为1×10-5 M~5×10-4 M；在激发波长分别为360nm和520nm的条件下，用于对水中的铁离子Fe3+和亚铁离子Fe2+进行选择性双激发比率式检测。
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