CN106883846B - 一种绝对水溶性的锌离子荧光探针、制备方法及其应用 - Google Patents
一种绝对水溶性的锌离子荧光探针、制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种绝对水溶性的锌离子荧光探针,其化学分子式为:C61H97O36N5,分子结构式为:
Description
技术领域
本发明属于分析化学技术领域,具体涉及一种绝对水溶性的锌离子荧光探针、制备方法及其应用。
背景技术
小分子荧光探针因其高灵敏性、高选择性和简便性是目前检测金属离子的前沿性研究课题。目前基于金属锌离子检测的荧光探针发展了一系列有机小分子,其中代表性的有机小分子为喹啉类和香豆素类衍生物。这些有机小分子荧光探针的局限性包括:1)合成过程较为繁琐;2)合成的有机小分子在锌离子的检测过程中需要有机溶剂的助溶,增加了检测体系毒性,限制了荧光探针在生物体系中的应用。
发明人以前合成了一个新的基于喹啉类的有机小分子(见发表文献,“A HighlySelective Turn-On Fluorescent Chemosensor for Zinc Ion in Aqueous Media”,Journal of fluorescence:2013, 23: 1239–1245)。这个有机小分子可以高效的检测出锌离子,具有较高的灵敏度和选择性。但是也存在着一些局限性:(1)这个有机小分子合成较为繁琐;(2)在锌离子的检测过程中需要部分有机溶剂才能将其溶解,不能在绝对水性环境中进行锌离子的检测。
发明内容
为解决上述问题,本发明提供一种绝对水溶性的锌离子荧光探针、制备方法及其应用,在锌离子有机小分子荧光探针的合成过程中引入β-环糊精,从而解决上述我们方法的两个个不足之处。利用四乙烯五胺-β-环糊精与萘酚甲醛的简单缩合,可以创新性地部分解决锌离子有机小分子荧光探针的合成繁琐和水溶性差的问题。
本发明的目的是以下述方式实现的:
一种绝对水溶性的锌离子荧光探针,其化学分子式为:C61H97O36N5,分子结构式为:
。
上述的绝对水溶性的锌离子荧光探针的制备方法,具体步骤如下:
(1)准确称量四乙烯五胺-β-环糊精和萘酚甲醛,将四乙烯五胺-β-环糊精溶解在水中,萘酚甲醛溶解在无水乙醇中;
(2)将步骤(1)所得溶液混合,在60-70℃条件下加热反应20-24h;
(3)反应结束后,除去溶剂,再向其中加入无水乙醇,即可析出权利要求1所述的锌离子荧光探针;
(4)抽滤,重结晶,干燥18-20h,得到纯度较高的权利要求1所述的锌离子荧光探针。
所述步骤(1)中四乙烯五胺-β-环糊精和萘酚甲醛的摩尔比为1:(1-1.2),溶剂水与无水乙醇的体积比为4:(1-1.5)。
上述的绝对水溶性的锌离子荧光探针的应用,绝对水溶性的锌离子荧光探针在水环境体系中锌离子含量的传感检测,所述的传感检测是荧光强度检测。
相对于现有技术,本发明基于四乙烯五胺-β-环糊精与萘酚甲醛简单缩合大大提高了锌离子有机小分子荧光探针的合成简便性,而合成过程中引入的β-环糊精化合物创新性地解决锌离子有机小分子荧光探针的水溶性问题,可以非常普适地应用于各种绝对水溶性有机小分子荧光探针的合成过程中。
附图说明
图1是四乙烯五胺环糊精及本发明合成的小分子荧光探针的红外光谱。
图2是本发明合成的小分子荧光探针的扫描电镜照片(×5K)。
图3是本发明合成的小分子荧光探针的扫描电镜照片(×100K)。
图4是本发明合成的小分子荧光探针的荧光选择光谱。
图5是锌离子对荧光探针的荧光滴定光谱。
图6是利用Benesi-Hildebrand方程拟合的荧光探针与锌离子的结合常数曲线。
图7是锌离子对荧光探针的紫外-可见滴定光谱。
具体实施方式
实施例1:
一种绝对水溶性的锌离子荧光探针,其化学分子式为:C61H97O36N5,分子结构式为:
。
上述的绝对水溶性的锌离子荧光探针的制备方法,具体步骤如下:
(1)准确称量四乙烯五胺-β-环糊精和萘酚甲醛,将四乙烯五胺-β-环糊精溶解在水中,萘酚甲醛溶解在无水乙醇中;
(2)将步骤(1)所得溶液混合,在60-70℃条件下加热反应20-24h;
(3)反应结束后,除去溶剂,再向其中加入无水乙醇,即可析出权利要求1所述的锌离子荧光探针;
(4)抽滤,重结晶,干燥18-20h,得到纯度较高的权利要求1所述的锌离子荧光探针。
本发明所述的水溶性锌离子荧光探针的合成过程如下:
所述步骤(1)中四乙烯五胺-β-环糊精和萘酚甲醛的摩尔比为1:(1-1.2),溶剂水与无水乙醇的体积比为4:(1-1.5)。
上述的绝对水溶性的锌离子荧光探针的应用,绝对水溶性的锌离子荧光探针在水环境体系中锌离子含量的传感检测,所述的传感检测是荧光强度检测。
实施例2:
准确称量四乙烯五胺-β-环糊精0.0325g与萘酚甲醛0.0045 g(摩尔比为1:1.05),将四乙烯五胺环糊精溶解在4 mL水中,然后将萘酚甲醛溶解在1.2mL无水乙醇中,在62℃条件下反应21h,然后利用旋转蒸发仪蒸去溶剂,然后向其中加入10 mL的无水乙醇,析出浅黄色固体,利用布氏漏斗抽滤,并用1:3的水/乙醇混合溶剂进行重结晶,然后在真空干燥箱中干燥18.5h,将得到的目标化合物。
实施例3:
准确称量四乙烯五胺-β-环糊精0.0325g与萘酚甲醛0.0047 g(摩尔比为1:1.1),将四乙烯五胺环糊精溶解在4 mL水中,然后将萘酚甲醛溶解在1.3mL无水乙醇中,在65℃条件下反应22h,然后利用旋转蒸发仪蒸去溶剂,然后向其中加入10 mL的无水乙醇,析出浅黄色固体,利用布氏漏斗抽滤,并用1:3的水/乙醇混合溶剂进行重结晶,然后在真空干燥箱中干燥19h,将得到的目标化合物。
实施例4:
准确称量四乙烯五胺-β-环糊精0.0325g与萘酚甲醛0.0050 g(摩尔比为1:1.15),将四乙烯五胺环糊精溶解在4 mL水中,然后将萘酚甲醛溶解在1.4mL无水乙醇中,在68℃条件下反应23h,然后利用旋转蒸发仪蒸去溶剂,然后向其中加入10 mL的无水乙醇,析出浅黄色固体,利用布氏漏斗抽滤,并用1:3的水/乙醇混合溶剂进行重结晶,然后在真空干燥箱中干燥19.5h,将得到的目标化合物。
实施例5:
准确称量四乙烯五胺-β-环糊精0.0325g与萘酚甲醛0.0052 g(摩尔比为1:1.2),将四乙烯五胺环糊精溶解在4 mL水中,然后将萘酚甲醛溶解在1.5mL无水乙醇中,在68℃条件下反应24h,然后利用旋转蒸发仪蒸去溶剂,然后向其中加入10 mL的无水乙醇,析出浅黄色固体,利用布氏漏斗抽滤,并用1:3的水/乙醇混合溶剂进行重结晶,然后在真空干燥箱中干燥20h,将得到的目标化合物。
实施例6:
准确称量四乙烯五胺-β-环糊精0.0325g与萘酚甲醛0.0043 g(摩尔比为1:1),将四乙烯五胺环糊精溶解在4 mL水中,然后将萘酚甲醛溶解在1mL无水乙醇中,在60℃条件下反应20h,然后利用旋转蒸发仪蒸去溶剂,然后向其中加入10 mL的无水乙醇,析出浅黄色固体,利用布氏漏斗抽滤,并用1:3的水/乙醇混合溶剂进行重结晶,然后在真空干燥箱中干燥18h,将得到的目标化合物利用熔点仪、红外光谱、核磁共振和紫外光谱等表征手段进行系统表征,确认所合成的化合物即为有机小分子荧光探针。产率:32%,熔点:273-274℃,H-NMR(DMSO-d 6 400 MHz): δ 1.21 (3H, m, -C16-H), δ 2.52-2.76 (2H, m, -C9-H), δ 2.98(1H, m, -C15-H), δ 3.09-3.28 (1H, m, -C2-H), δ 3.32-3.42 (1H, m, -C4-H), δ3.45-3.64 (2H, m, -C3-H, -C5-H), δ 3.80-3.85 (2H, m, -C6-H), δ 4.82 (1H, m, -C1-H). δ 5.75-5.93 (1H, m, -C11-H), δ 6.78-6.89 (1H, m, -C13-H), δ 7.17 (1H, s,-C12-H), δ 7.40 (1H, s, -C15-H),δ 7.66-7.72 (1H, m, -C14-H),δ 8.03-8.18 (1H, m,-C16,17-H), δ 9.25-9.47 (1H, m, -O18-H)。
该反应的化学方程式如下:
合成的锌离子荧光探针的分子缩写及核磁共振中对应的原子编号如下所示:
图1为原料四乙烯五胺环糊精及合成的小分子荧光探针的红外光谱,可以看到在1502 cm-1处出现了–C=N–的红外吸收峰,说明目标分子的成功合成。
图2-3为合成的小分子荧光探针的扫描电镜照片,可以看到合成小分子荧光探针形貌并不规整,另外在体系中含有一些孔道结构。
荧光探针对锌离子的检测过程:
将本发明合成的有机小分子荧光探针溶解在纯水体系中(不含有机溶剂),利用HEPES缓冲溶液控制体系的pH值为7.2,研究此小分子荧光探针对各种金属离子的荧光选择性,荧光选择性实验证明此有机小分子荧光针对锌离子有特殊的荧光响应性,而对其他金属离子没有响应,是可以在纯水体系中检测锌离子的荧光探针,另外荧光竞争实验可以进一步进行证明,同时为了直观说明这个有机小分子荧光探针对锌离子的荧光选择性,利用在紫外灯下的荧光图像可以清楚地看到没有加入锌离子的有机小分子荧光探针溶液没有明显的荧光,而加入锌离子后,有强的蓝色荧光,结果如图4所示。
图4为合成的荧光谈针对金属离子的荧光选择光谱,在纯水体系中荧光探针对浓度相同的各种金属离子(Al3+,Zn2+,Cu2+,Cd2+,Hg2+, Mg2+,Na+,Mn2+,Co2+,Fe3+)的荧光变化图谱可以看到,荧光探针对锌离子具有很高的荧光选择性,对锌离子的荧光响应敏感性要远远大于对其他金属离子的荧光响应性能。因此,本发明合成的小分子荧光探针对锌离子具有特异性地识别效果。
将合成荧光探针溶解在纯水中,配置成1 mM的纯水溶液,在HEPES(pH=7.2)纯水体系中测试其荧光光谱和紫外可见光谱,结果如图5-7所示。
图5-6为锌离子对荧光探针的荧光滴定光谱及利用Benesi-Hildebrand方程(如下)计算的结合常数,计算得到锌离子与荧光探针在纯水体系中的结合常数为1.50 × 1012M-1,另外根据荧光光谱得到荧光探针对锌离子的检测限达到0.1 ppm数量级。
Benesi-Hildebrand方程:。
图7为锌离子对荧光探针的紫外-可见滴定光谱,随着金属离子的加入,紫外吸收光谱在400 nm处的吸收峰发生了明显的红移。
以上所述的仅是本发明的优选实施方式,应当指出,对于本领域的技术人员来说,在不脱离本发明整体构思前提下,还可以作出若干改变和改进,这些也应该视为本发明的保护范围。
Claims (4)
1.一种水溶性的锌离子荧光探针,其特征在于:其化学分子式为:C61H97O36N5,分子结构式为:
。
2.如权利要求1所述的水溶性的锌离子荧光探针的制备方法,其特征在于:具体步骤如下:
(1)准确称量四乙烯五胺-β-环糊精和萘酚甲醛,将四乙烯五胺-β-环糊精溶解在水中,萘酚甲醛溶解在无水乙醇中;
(2)将步骤(1)所得溶液混合,在60-70℃条件下加热反应20-24h;
(3)反应结束后,除去溶剂,再向其中加入无水乙醇,即可析出上述的锌离子荧光探针;
(4)抽滤,重结晶,干燥18-20h,得到上述的锌离子荧光探针。
3.根据权利要求2所述的水溶性的锌离子荧光探针的制备方法,其特征在于:所述步骤(1)中四乙烯五胺-β-环糊精和萘酚甲醛的摩尔比为1:(1-1.2),溶剂水与无水乙醇的体积比为4:(1-1.5)。
4.如权利要求1所述的水溶性的锌离子荧光探针的应用,其特征在于:水溶性的锌离子荧光探针在水环境体系中锌离子含量的传感检测,所述的传感检测是荧光强度检测。
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A facile synthesis of a highly water-soluble and selective fluorescent sensor towards zinc ions derived from b-cyclodextrin based on an unexpected sensing process;Zengchen Liu等;《RSC Adv.》;20151124;第5卷;100482-100487 |
水溶性环糊精主-客体自组装荧光探针的制备及锌离子识别研究;刘增臣 等;《中国化学会第30届学术年会摘要集-第七分会:无机化学前沿》;20160701;1 |
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