阴离子诱导三联吡啶铂(II)配合物3MMLCT发射: 核苷酸的高效识别

doi:10.6023/cjoc202502013

摘要/Abstract

研究了三联吡啶铂(II)配合物P-1在磷酸根阴离子诱导下的聚集行为, 并用于结构类似化合物腺苷酸三磷酸盐(ATP)、腺苷酸二磷酸盐(ADP)和腺苷酸单磷酸盐(AMP)分子的高效识别. 在荧光光谱和紫外可见吸收光谱中, 配合物P-1与不同磷酸根阴离子通过分子间的π-π作用、Pt…Pt作用和静电作用发生聚集, 进而产生不同的¹MMLCT吸收和³MMLCT发射, 这些微妙的光谱差异可以将配合物P-1用于识别不同的磷酸根阴离子. 更重要的是, 手性小分子化合物ATP和ADP可以诱导P-1聚集, 在300~500 nm处分别产生向上和向下的圆二色信号, 而AMP则无法诱导P-1产生聚集, 故无圆二色信号, 从而实现对ATP、ADP和AMP高效识别. 这一发现为识别结构相似的核苷酸分子(如ATP、ADP和AMP)提供了一种新颖且高效的方法.

关键词: 联吡啶铂(II)配合物, 核苷酸, 分子识别

This study investigated the aggregation behavior of the terpyridine platinum(II) complex P-1 induced by various anions, which was used for identifying structurally similar molecules of adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP). The complex P-1 was found to form different aggregates under different anions, facilitated by intermolecular π-π interactions, Pt…Pt interactions, and electrostatic interactions, resulting in different¹MMLCT absorption and ³MMLCT emission signals, which was utilized for the recognition of various phosphate anions. Moreover, it was found that structurally similar nucleotides ATP and ADP induced different aggregation behavior for P-1 and resulted positive and negative circular dichroism signals at 300~500 nm, respectively, while AMP didn’t induce aggregation and therefore had silent circular dichroism signals. Thus, ATP, ADP, and AMP were effectively identified using circular dichroism spectroscopy which was much more effective than using absorption and emission spectra that based on the intensity change.

Key words: tripyridine-platinum(Ⅱ) complex, nucleotides, molecular identification

引用此文

刘金波, 郭倩, 杨成, 伍晚花. 阴离子诱导三联吡啶铂(II)配合物³MMLCT发射: 核苷酸的高效识别[J]. 有机化学, 2025, 45(11): 4227-4233.

Jinbo Liu, Qian Guo, Cheng Yang, Wanhua Wu. Anion-Induced ³MMLCT Emission of Tripyridine-Platinum Complex: Efficient Identification of Nucleotides[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4227-4233.

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图/表 8

图式1. ATP、ADP和AMP的化学结构式

Scheme 1. Structures of nucleic acid molecules ATP, ADP and AMP

图式2. 配合物P-1的合成路线

Scheme 2. Synthesis of the metal complex P-1

图1. P-1在DMSO溶液中随含水量(0~100%)变化的紫外可见吸收光谱图

Figure 1. UV-vis absorption spectra of P-1 in DMSO solution with increasing water content from 0 to 100% [P-1]=60 μmol/L, 298 K

图2. 在P-1水溶液中加入不同浓度的ATP时吸收光谱(a)和发射光谱(b)的变化

Figure 2. UV-Vis (a) and emission spectral (b) changes of P-1 with different concentrations of ATP Solvent: water, [P-1]=120 μmol/L, λex=440 nm

图3. 不同磷酸衍生物作用下化合物P-1的吸收光谱(a)和640 nm处的吸收变化谱图(b)

Figure 3. UV-vis spectra (a) and changes of absorbance at 640 nm (b) of P-1 with different phosphate derivatives c=30 μmol/L, solvent: water, 298 K

图4. 加入不同磷酸衍生物条件下化合物P-1的荧光光谱(a)和850 nm处的发射强度变化图(b)

Figure 4. Emission spectra (a) and changes of emission at 850 nm (b) of P-1 with different phosphate derivative c=30 μmol/L, solvent: water, λex=440 nm, 298 K

Compd.	λ_abs/nm	Abs^b	A/A₀^c	λ_em^d/nm	I/I₀^e
P-1	472	0.011	1.0	859	1.0
P-1＋ATP	472/640	0.052	4.5	836	14.1
P-1＋ADP	472/640	0.044	3.8	821	9.1
P-1＋AMP	472	0.013	1.1	859	1.0
P-1＋triPPi	476/642	0.044	3.8	844	9.2
P-1＋PPi	476/642	0. 039	3.4	848	4.8
P-1＋Pi	476	0.009	0.8	859	0.9

表1. 不同磷酸根阴离子诱导P-1聚集的光物理性质a

Table 1. Photophysical properties of P-1 aggregation induced by different anions

图5. 不同磷酸衍生物下化合物P-1的圆二色光谱图

Figure 5. CD spectra of P-1 with different phosphate derivatives c=60 μmol/L, solvent: water, 298 K

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阴离子诱导三联吡啶铂(II)配合物³MMLCT发射: 核苷酸的高效识别

Anion-Induced ³MMLCT Emission of Tripyridine-Platinum Complex: Efficient Identification of Nucleotides

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