新型水溶性中氮茚衍生物的合成及铜离子荧光探针行为

doi:10.7503/cjcu20140592

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (2): 287.doi: 10.7503/cjcu20140592

新型水溶性中氮茚衍生物的合成及铜离子荧光探针行为

孔伟伟, 江玉亮, 韩巧荣, 王炳祥()

江苏省生物功能材料重点实验室, 江苏省生物医药功能材料工程研究中心,南京师范大学化学与材料科学学院, 南京 210097

收稿日期:2014-06-27 出版日期:2015-02-10 发布日期:2014-12-30
作者简介:联系人简介: 王炳祥, 男, 博士, 教授, 主要从事有机化学研究. E-mail: wangbingxiang@njnu.edu.cn
基金资助:
国家自然科学基金(批准号: 21202101)、高等学校国家级大学生创新创业训练计划项目(批准号: 201310319053Z)和江苏高校优势学科建设工程项目资助

Synthesis of New Water-soluble Derivatives of Indolizine and Their Applications as Fluorescence Sensors for C $u 2 + †$

KONG Weiwei, JIANG Yuliang, HAN Qiaorong, WANG Bingxiang^*()

Jiangsu Province Key Laboratory of Biofunctional Materials, Jiangsu Province Engineering Research Center for Biomedical Functional Material, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210097, China

Received:2014-06-27 Online:2015-02-10 Published:2014-12-30
Contact: WANG Bingxiang E-mail:wangbingxiang@njnu.edu.cn
Supported by:
Supported by the National Natural Science Foundation of China(No.21202101), the National University Students’ Innovative Training Program Foundation of China(No.201310319053Z) and the Project Funded by the Priority Academic Program Development of Jiangsu Higher Eduacation Institutions, China

摘要/Abstract

摘要：

设计合成了2个新型水溶性中氮茚季铵盐化合物4a{氯化2-[N'-(3-氰基-中氮茚-1-甲酰基)肼基] 酰乙基-1-吡啶鎓盐}和4b{氯化2-[N'-(3-氰基-中氮茚-1-甲酰基) 肼基]酰乙基-1-(2-甲基吡啶)鎓盐}, 采用红外光谱、核磁共振、质谱和元素分析对其进行了结构表征, 并研究了它们的光谱性质. 选取Cu²⁺, Zn²⁺, Ca²⁺, Cr³⁺, Co²⁺, Al³⁺, Mn²⁺, Ni²⁺, Ba²⁺, Hg²⁺, Fe³⁺, Cd²⁺, Mg²⁺, Pb²⁺, Li⁺和Ag⁺等16种常见金属离子, 对2个化合物进行了离子识别实验. 结果表明, 化合物4a和4b在一定浓度范围内对铜离子均具有良好的选择性识别能力, 受常见离子干扰小. 由于空间位阻的影响, 化合物4a具有比4b更高的灵敏性.

关键词: 中氮茚季铵盐, 铜离子, 荧光探针

Abstract:

Two new quaternary ammonium salts of indolizine derivatives 4a(1-{2-[N'-(3-cyano- indolizine-1-carbonyl)-hydrazino]-2-oxo-ethyl}-pyridinium; chloride) and 4b(1-{2-[N'-(3-Cyano-indolizine-1-carbonyl)-hydrazino]-2-oxo-ethyl}-2-methyl-pyridinium; chloride) as fluorescent sensors for Cu²⁺ were synthesized. The structures of the two compounds were determined by IR, ¹H NMR, MS and elemental analysis. Their UV and fluorescence spectra were measured. The influences of sixteen metal ions such as Cu²⁺, Zn²⁺, Ca²⁺, Cr³⁺, Co²⁺, Al³⁺, Mn²⁺, Ni²⁺, Ba²⁺, Hg²⁺, Fe³⁺, Cd^{2 +}, Mg²⁺, Pb²⁺, Li⁺ and Ag⁺on their fluorescence properties were studied. Spectroscopic studies revealed that the two compounds had rather strong affinity toward Cu²⁺. The specificities of the two probes toward Cu²⁺were determined. Compound 4a nearly no fluorescence intensity changes were observed in emission spectra together with Zn²⁺, Ca²⁺, Co²⁺, Mn²⁺, Ni²⁺, Ba²⁺, Hg²⁺,Cd²⁺, Mg²⁺, Pb²⁺, Li⁺ and Ag⁺, respectively. Compound 4b nearly no fluorescence intensity changes were observed in emission spectra together with Zn²⁺, Ca²⁺, Cr³⁺, Co²⁺, Al³⁺, Mn²⁺, Ni²⁺, Ba²⁺, Hg²⁺, Cd²⁺, Mg²⁺, Pb²⁺, Li⁺and Ag⁺, respectively. However, under identical conditions, the results showed that compounds 4a and 4b had fluorescence quenching together with Cu²⁺. So we have developed two new fluorescent sensors(4a and 4b). They showed high sensitivity and selectivity toward Cu²⁺ in aqueous solution.

Key words: Quaternary ammonium salt of indolizine derivative, Cu2+ ion, Fluorescent sensor

中图分类号:

O626
O613.71

TrendMD:

孔伟伟, 江玉亮, 韩巧荣, 王炳祥. 新型水溶性中氮茚衍生物的合成及铜离子荧光探针行为. 高等学校化学学报, 2015, 36(2): 287.

KONG Weiwei, JIANG Yuliang, HAN Qiaorong, WANG Bingxiang. Synthesis of New Water-soluble Derivatives of Indolizine and Their Applications as Fluorescence Sensors for C $u 2 + †$ . Chem. J. Chinese Universities, 2015, 36(2): 287.

图/表 11

Scheme 1 Synthetic routes of compounds 4a and 4b

Table 1 Appearance, yields, melting points and elemental analysis for compounds 4a and 4b

Compd.	Appearance	Yield(%)	m. p./℃	LC-MS, ([M-Cl]⁺), m/z	Elemental analysis(%, calcd.)
Compd.	Appearance	Yield(%)	m. p./℃	LC-MS, ([M-Cl]⁺), m/z	C	H	N
4a	White crystal	77	283—284	320.0	57.27(57.39)	3.99(3.97)	19.72(19.68)
4b	White crystal	75	286—288	334.0	58.42(58.46)	4.40(4.36)	18.90(18.94)

Table 2 1H NMR, IR and LC-MS data for compounds 4a and 4b

Compd.	¹H NMR(400 MHz, D₂O), δ	IR(KBr), $ν ˙$ /cm^-1
4a	8.55—8.89(m, 4H, ArH), 8.02—8.07(m, 2H, ArH), 6.75—7.38(m, 4H, ArH), 5.58(s, 2H, CH₂)	3441, 3228, 3171, 2997, 2198, 1705, 1665, 1510, 1226, 762
4b	9.07(d, J=8.1 Hz, 1H, ArH), 8.68(d, J=4.8 Hz, 1H, ArH), 7.83—8.39(m, 3H, ArH), 7.53—7.59(m, 2H, ArH), 6.92—7.26(m, 2H, ArH), 5.55(s, 2H, CH₂), 2.75(s, 3H, CH₃)	3478, 3230, 3105, 2950, 2197, 1698, 1625, 1510, 1220, 751

Table 2 1H NMR, IR and LC-MS data for compounds 4a and 4b

Compd.	¹H NMR(400 MHz, D₂O), δ	IR(KBr), $ν ˙$ /cm^-1
4a	8.55—8.89(m, 4H, ArH), 8.02—8.07(m, 2H, ArH), 6.75—7.38(m, 4H, ArH), 5.58(s, 2H, CH₂)	3441, 3228, 3171, 2997, 2198, 1705, 1665, 1510, 1226, 762
4b	9.07(d, J=8.1 Hz, 1H, ArH), 8.68(d, J=4.8 Hz, 1H, ArH), 7.83—8.39(m, 3H, ArH), 7.53—7.59(m, 2H, ArH), 6.92—7.26(m, 2H, ArH), 5.55(s, 2H, CH₂), 2.75(s, 3H, CH₃)	3478, 3230, 3105, 2950, 2197, 1698, 1625, 1510, 1220, 751

Fig.1 UV-Vis absorption spectra of compounds 4a(A) and 4b(B)

Table 3 Fluorescence properties of compounds 4a and 4b

Compd.	λ_em/nm	τ_f/ns	φ_f
4a	380	1.4	0.28
4b	379	2.2	0.34

Table 4 Fluorescence intensities of compound 4a in different pH value solutions(λex=290 nm, silt=5×5)

pH	1.12	2.10	3.12	4.46	5.99	6.90	7.02	7.12	7.80	8.64	10.01	11.70	12.85
λ_em/nm	381	381	380	380	380	380	379	379	379	378	378	379	378
I_f/a.u.	230	220	215	202	196	181	160	159	154	124	88	60	48

Table 5 Fluorescence intensities of compound 4b in different pH value solutions(λex=295 nm, silt=5×5)

pH	1.26	2.20	3.19	4.96	5.59	6.55	6.82	7.12	7.96	8.27	9.86	11.81	12.82
λ_em/nm	381	381	380	380	380	380	379	379	379	378	378	No peak	No peak
I_f/a.u.	240	221	227	230	234	192	203	192	188	180	77

Fig.2 Fluorescence intensities of compounds 4a(A) and 4b(B) with different metal ions(λex=290 nm) a. Blank; b. Cu2+; c. Zn2+; d. Al3+; e. Ni2+; f. Li+; g. Cd2+; h. Ba2+; i. Mn2+; j. Co2+; k. Ca2+; l.Cr3+; m. Ag+; n. Fe3+; o. Pb2+; p. Mg2+; q. Hg2+.

Fig.3 Fluorescence spectra of compound 4a(A) and 4b(B)(1.0×10-5 mol/L) upon addition of different concentration of Cu2+Insets show the linear relationships of PL intensity versus the concentration of Cu2+ over the range from 0 to 25 μmol/L. c(Cu2+)/(μmol·L-1), (A) a—h: 0, 5, 10, 15, 20, 25, 30, 35; (B) a—f: 0, 5, 10, 15, 20, 25.

Fig.4 Fluorescence intensities of compounds 4a(A) and 4b(B) with Cu2+and other ions in water1.None; b. Cu2+; c. Cu2++Na+; d. Cu2++K+; e. Cu2++Ca2+; f. Cu2++Zn2+; g. Cu2++Mg2+; h. Cu2++Hg2+; i. Cu2++Fe3+; j. Cu2++Al3+.

Fig.5 Possible coordination structures of compounds 4a and 4b to Cu2+

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新型水溶性中氮茚衍生物的合成及铜离子荧光探针行为

Synthesis of New Water-soluble Derivatives of Indolizine and Their Applications as Fluorescence Sensors for C $u 2 + †$

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新型水溶性中氮茚衍生物的合成及铜离子荧光探针行为

Synthesis of New Water-soluble Derivatives of Indolizine and Their Applications as Fluorescence Sensors for Cu2+†

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Synthesis of New Water-soluble Derivatives of Indolizine and Their Applications as Fluorescence Sensors for C $u 2 + †$