CN103224509A - 一种氟硼荧光衍生物、其制备方法及应用 - Google Patents
一种氟硼荧光衍生物、其制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种氟硼荧光衍生物、其合成方法与应用,属金属离子检测领域。其分子结构式如下:,该类氟硼荧光衍生物用于环境中的镉离子的荧光传感、分析,识别镉离子后,硼原子可以和镉离子发生交换,对镉离子选择性好,对其他金属离子抗干扰能力强,可以避免其它金属离子的干扰,特别是锌离子的干扰,可以快速灵敏地从多种金属离子中区分镉离子。
Description
技术领域
本发明涉及一种氟硼荧光衍生物及其合成方法与应用,属金属离子检测领域。
背景技术
镉在自然环境中以氧化物或者盐的形式存在于矿物质中,在化肥和镉镍电池等工业生产领域大量使用,由其造成的环境污染越来越严重。镉流失到环境中容易通过食物进入生物体或人体,镉在人体积蓄作用,潜伏朗可长达10~30年,日积月累,给生物体或人体造成危害。据报道,当水中镉超过0.2mg/L时,居民长期饮水和从食物中摄取含镉物质,可引起“骨痛病”。金属镉毒性很低,但其化合物毒性很大。
因此,对于镉离子的检测十分重要,传统的检测方法包括原子吸收光谱法、紫外分光光度法、伏安法等方法。其中使用荧光探针的方法具有灵敏度高、选择性好、原位检测、相应速度快等特点,非常适于检测镉离子。而对于镉离子的荧光检测方面最主要的一个问题就是与锌离子的区分问题。由于镉离子和锌离子在同一族,其离子的化学性质极为相似,研究新型的镉离子荧光探针具有十分重要的意义。
发明内容
本发明目的在于提供一种高选择性、高灵敏度的氟硼荧光衍生物,用于镉离子检测;另一目的在于提供其制备方法。
该镉离子的荧光探针是氟硼荧光衍生物。其分子结构式如下:
式中R为C1-4烷基。
R优选C1-2烷基。
其制备方法如下:
(a) 将3-硝基苯磺酸钠、硼酸和七水合硫酸亚铁加入到质量百分比98%硫酸中。冷却,将甘油、2-胺基-6-甲基吡啶和热水缓慢加入上述混合物中。加热回流冷至室温。调节pH值,用氯仿溶解有机相,并通过柱层析进行提纯得到化合物1。
(b) 将步骤(a)所得化合物1和SeO2加入至1,4-二氧六环中,在氮气保护下回流后过滤。滤液真空干燥过柱得到化合物2。
(c) 将步骤(b)得到的化合物2及亚硫酸氢钠和取代的邻苯二胺,在氮气保护下在乙醇溶液中反应。真空干燥过柱得到化合物3。
(d) 室温下将三氟化硼乙醚缓慢加入化合物3的氯仿溶液中搅拌得到目标物4。
所述的取代的邻苯二胺与目标产物4的R一致。
本发明设计、合成的荧光探针其结构特点是苯并咪唑与萘啶分子以单键联接,苯并咪唑上的一个氮原子和萘啶基团的一个氮原子与硼以化学键联接。硼原子可以和镉离子发生交换从而引起荧光变化,而其他包括锌离子在内的金属离子则不会和荧光探针发生作用引起荧光变化,从而可以避免其它金属离子的干扰,特别是锌离子的干扰。可以快速灵敏地从多种金属离子中区分镉离子,用于环境中的镉离子的荧光传感、分析。
本发明氟硼化合物对镉离子的识别作用原理:
附图说明
图1:本发明氟硼荧光衍生物识别Cd2+后的晶体结构图;
图2:本发明实施例制得的氟硼荧光衍生物在乙醇中的紫外可见吸收光谱;
图3:加入CdCl2后,本发明实施例制得的氟硼荧光衍生物的乙醇溶液(2.0 × 10–5 M)的荧光发射光谱变化。激发波长357 nm。插入:在365 nm照射下,本发明氟硼荧光衍生物的乙醇溶液(2.0 × 10–5 M)的照片(左:只有本发明氟硼荧光衍生物,右:加入Cd2+);
图4:在乙醇溶液中加入不同金属阳离子后本发明实施例制得的氟硼荧光衍生物的荧光光谱变化;图中1为加入Cd2+荧光光谱变化,2为加入Na+,Mg2+,Al3+,K+,Ca2+,Cr3+,Mn2+,Fe3+,Co2+,Ni2+,Cu2+,Zn2+,Hg2+,Pb2+荧光光谱变化;
图5:本发明实施例制得的氟硼荧光衍生物 (2.0 × 10–5 M)在加入CdCl2后紫外可见光谱变化;
图6:加入Cd2+后本发明实施例制得的氟硼荧光衍生物(2.0 × 10–5 M)在485 nm处的荧光光谱强度随Cd2+浓度变化情况;
图7:本发明实施例制得的氟硼荧光衍生物(2.0 × 10–5 M)的乙醇溶液加入不同金属的盐(盐的离子的比例为1.2当量,黑条)和本发明实施例制得的氟硼荧光衍生物中加入Cd2+后再加入适当的金属离子(本发明实施例制得的氟硼荧光衍生物和其他盐离子的比率是1.2当量,灰柱)的荧光变化。激发波长为357 nm。I和I0代表在485 nm处的发光强度。金属盐指氯化钠,氯化镁,硝酸铝,氯化钾,氯化钙,氯化铬,氯化锰,氯化铁,氯化钴,氯化镍,氯化铜,氯化锌,氯化镉,氯化汞和氯化铅。
具体实施方式
实施例 本发明所述氟硼化合物具有如下结构:
其按照下列步骤进行制备:
(a) 将3-硝基苯磺酸钠(17.5 g, 77.7 mmol)、硼酸(2.4 g, 38.8 mmol)和七水合硫酸亚铁(1.4 g, 0.5 mmol)加入到23.1 mL质量百分比 98%硫酸中。冷却至0 °C,将甘油(12.5 mL),2-胺基-6-甲基吡啶(4.3 g,40.0 mmol)和热水(50 °C, 22.5 mL)缓慢加入上述混合物中。加热至135 °C回流4个小时冷至室温。调节pH值,用氯仿溶解有机相,并通过柱层析进行提纯(200?300 mesh)得到产物。
表征如下:1H NMR: δH (400 MHz; CDCl3; Me4Si) 9.08(d, 1H), 8.15 (m, 1H), 8.08(d, 1H), 7.42 (m, 1H), 7.28 (d, H), 2.82 (s, 3H). 13C NMR: δC (100 MHz, CDCl3): 163.06, 155.96, 153.31, 136.86, 136.65, 123.03, 121.37, 120.76, 25.72.
(b) 上步所得产物(1.1592 g, 8.0 mmol)和SeO2(1.2452 g, 11.2 mmol)加入至20 mL 1,4-二氧六环中。在氮气保护下回流4小时后过滤。滤液真空干燥过柱(200?300 mesh, ethyl acetate)得到产物。
表征如下:1H NMR: δH (400 MHz; DMSO; Me4Si) 10.15(s, 1H), 9.25 (m, 1H), 8.71 (d, 1H), 8.61 (m, 1H), 8.08 (d, 1H), 7.78 (m, 1H). 13C NMR: δC (100 MHz, DMSO): 194.32, 155.77, 155.49, 154.95, 140.47, 138.30, 125.58, 124.87, 118.46.
(c) 将上步得到的产物,NaHSO3和2-甲基邻苯二胺在氮气保护下10 mL乙醇溶液中反应8小时。真空干燥过柱得到产物。
表征如下:HRMS (EI) m/z: calcd for C16H12N4 [M + H]+, 261.1062; found, 261.1142. 1H NMR: δH (400 MHz; DMSO-d6; Me4Si) 13.47(s, 0.33H), 13.43(s, 0.65H), 9.17 (m, 1H), 8.63 (m, 2H), 8.56 (d, 1H), 7.69 (m, 1H), 7.62 (d, 0.3H), 7.43 (d, 0.7H), 7.18 (m, 1H), 7.07 (m, 1H), 2.65 (s, 3H). 13C NMR: δC (100 MHz, DMSO-d 6): 155.79, 154.87, 154.77, 152.24, 152.00, 150.91, 149.99, 144.25, 143.96, 139.52, 139.41, 138.13, 135.43, 124.95, 124.29, 123.43, 123.19, 123.15, 122.80, 122.71, 120.87, 120.62, 117.53, 110.38, 99.98, 17.88, and 17.14.
(d) 室温下将三氟化硼乙醚(0.2 mL, 1.6 mmol)缓慢加入10 mL上步产物的氯仿溶液中搅拌1小时得到最终产物。
表征如下:HRMS (EI) m/z: calcd for C16H11BF2N4 [M–BF2+2H]+, 261.1062; found, 261.1145. 1H NMR: δH (400 MHz; DMSO-d 6; Me4Si) 9.31 (m, 1H), 8.94 (d, 1H), 8.70 (m, 2H), 7.87 (m, 1H), 7.70 (d, 1H), 7.52 (m, 1H), 7.41 (m, 1H), 2.73 (s, 3H).13C NMR: δC (100 MHz, DMSO-d6): 185.53, 155.80, 154.70, 147.79, 146.70, 141.00, 139.07, 133.26, 127.15, 126.98, 126.15, 124.68, 124.50, 121.37, 112.41, and 17.35.
本发明氟硼荧光衍生物识别了镉离子后表征如下:HRMS (EI) calcd. for C32H24CdCl2N8 [1/2M–1/2CdCl2+H]+, 261.1062; found, 261.1130. 1H NMR: δH (400 MHz; DMSO; Me4Si) 13.45(s, 0.69H), 13.42 (s, 1.31H), 9.16 (m, 1H), 8.58 (m, 6H), 7.69 (m, 2H), 7.58 (d, 0.91H), 7.41 (d, 1.44H), 7.16 (m, 2H), 7.08 (m, 2H), 2.64 (s, 6H).。
表1:本发明氟硼荧光衍生物识别Cd2+后的晶体数据
Empirical formula | C32H24CdCl2N8O |
Formula weight | 719.90 |
Crystal size [mm] | 0.20×0.15×0.14 |
Crystal system | orthorhombic |
Space group | P c c n |
a [?] | 8.8201(3) |
b [?] | 15.1311(5) |
c [?] | 22.3128(7) |
α [deg] | 90.00 |
β [deg] | 90.00 |
γ [deg] | 90.00 |
Volume [?3], Z | 2977.82(17), 4 |
Dcalcd. [g/cm3] | 1.536 |
μ [mm-1], F (000) | 0.949, 1340.0 |
Reflections collected | 27210 |
Unique reflections | 2626 |
Rint | 0.0645 |
Final R indices | R1 = 0.0483 |
[I>2σ(I)]a | wR2 = 0.0872 |
R indices | R1 = 0.1074, wR2 = 0.1194 |
Goodness-of-fit on F 2 | 1.033 |
结合附图可以看出,氟硼荧光衍生物作为镉离子的荧光探针,用于环境中的镉离子的荧光传感、分析,能很好地避免其它金属离子的干扰,特别是锌离子的干扰,可以快速灵敏地从多种金属离子中区分镉离子。
Claims (4)
1.一种氟硼荧光衍生物,其特征在于,其结构式如下:
式中R为C1-4烷基。
2.如权利要求1所述的氟硼荧光衍生物,其特征在于,R优选C1-2烷基。
3.制备如权利要求1所述的氟硼荧光衍生物的方法,其特征在于,通过以下步骤实现:
(a) 将3-硝基苯磺酸钠、硼酸和七水合硫酸亚铁加入到质量百分比98%硫酸中,冷却;将甘油、2-胺基-6-甲基吡啶和热水缓慢加入上述混合物中;加热回流冷至室温,调节pH值,用氯仿溶解有机相,并通过柱层析进行提纯得到产物1;
(b) 将所得产物1和SeO2加入至1,4-二氧六环中,在氮气保护下回流后过滤,滤液真空干燥过柱得到产物2;
(c) 将产物2、亚硫酸氢钠和取代的邻苯二胺在氮气保护下在乙醇溶液中反应,真空干燥过柱得到最产物3;
(d) 室温下将三氟化硼乙醚缓慢加入产物3的氯仿溶液中搅拌得到目标产物4;
所述的取代的邻苯二胺与目标产物4的R一致。
4.根据权利要求1或2所述的氟硼荧光衍生物的用途,其特征在于,将其用于环境中的镉离子的荧光传感、分析。
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CN106045996A (zh) * | 2016-06-13 | 2016-10-26 | 贵州大学 | 一种2‑(2’‑羟基苯乙烯基)萘啶探针试剂及其制备和应用 |
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CN106045996A (zh) * | 2016-06-13 | 2016-10-26 | 贵州大学 | 一种2‑(2’‑羟基苯乙烯基)萘啶探针试剂及其制备和应用 |
CN106045996B (zh) * | 2016-06-13 | 2018-06-19 | 贵州大学 | 一种2-(2’-羟基苯乙烯基)萘啶探针试剂及其制备和应用 |
CN105949190A (zh) * | 2016-07-04 | 2016-09-21 | 烟台凯博医药科技有限公司 | 一种制备1,8-萘啶及衍生物的方法 |
CN106045997A (zh) * | 2016-07-04 | 2016-10-26 | 烟台凯博医药科技有限公司 | 2‑羟基‑1,5‑萘啶的制备方法 |
CN106045997B (zh) * | 2016-07-04 | 2019-02-26 | 烟台凯博医药科技有限公司 | 2-羟基-1,5-萘啶的制备方法 |
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