含哌嗪基团锌离子探针的双光子吸收增强机理

doi:10.6023/A23050248

摘要/Abstract

为了探寻锌离子配位诱导的双光子吸收增强机理, 采用分子动力学和量子化学方法, 研究了探针及其锌配合物的双光子吸收性质. 模拟了溶液中探针的结构演化和锌离子配位过程, 发现存在单配位和双配位两种配位模式, 与探针相比, 锌配合物主体平面性增强, 结构更稳定. 基于模拟结构, 采用量子化学方法优化了一系列探针和两种配位模式下的配合物结构, 并应用响应理论方法和两态模型计算了双光子吸收性质, 分析了分子内电荷转移过程. 结果表明, 配位模式和哌嗪结构对双光子吸收有重要影响. 单配位模式下, 当哌嗪环发生扭曲时, 双光子吸收截面增大, 波长几乎不变. 双配位模式下, 锌配合物的双光子吸收截面普遍减小, 波长发生蓝移. 通过对模拟结构进行采样, 计算了探针和两种配位模式下配合物的平均双光子吸收谱, 讨论了结构动态变化对双光子吸收性质的影响. 由于探针结构更加灵活, 导致平均双光子吸收降低, 从而使单配位模式下锌配合物的平均双光子吸收显著增强. 因此, 特殊的单配位结构和灵活的探针结构共同作用, 产生了配位后双光子吸收增强现象. 该研究有助于理解和预测双光子锌离子探针的光物理性质.

关键词: 双光子吸收, 锌离子, 哌嗪, 探针, 配位模式, 分子动力学

Zinc ion is an essential component in enzymes and proteins and involves in many biological processes. Although many two-photon zinc ion probes have been synthesized and applied for detecting the zinc ion, the related theoretical study is still in the primary stage. To explore the mechanism of coordination induced two-photon absorption (TPA) enhancement for a piperazine-based zinc ion probe, molecular dynamics simulations in combination with quantum chemical calculations are employed to calculate the TPA properties of the probe and its coordination complexes. The configuration evolution of the probe and the coordination process in water are investigated by molecular dynamics simulations. It is found that there are two coordination modes, which include mono-coordinated mode and bi-coordinated mode, to form zinc complexes. In comparison with the probe, the coordination complexes have more planar backbones and more stable structures. On the basis of the simulated configurations, a series of geometries for the probe and the zinc complexes with two coordination modes are optimized by quantum chemical methods and their TPA properties are calculated by the response theory and two-state model. The results show that the coordination mode and the structure of piperazine unit have important effects on TPA. The twisted piperazine ring in the mono-coordinated complex is very beneficial for improving the strength of TPA without changing the wavelength. The bi-coordination always decreases TPA and produces a blue-shifted wavelength. Through configurational sampling, the averaged TPA spectra for the probe and the complexes are calculated and the influence of the structural flexibility is analyzed. Because the probe has a more flexible structure, its averaged TPA intensity decreases, and then the great increase of TPA can be observed in the zinc complexes with mono-coordinated mode. Therefore, it is the special complex with mono-coordinated mode and the flexibility of the probe that produce the TPA enhancement after coordination in experiment. The present research would be helpful for understanding and predicting of the photophysical properties for two-photon zinc ion probes.

Key words: two-photon absorption, zinc ion, piperazine, probe, coordination mode, molecular dynamics

引用此文

赵珂, 程夏宇, 马雪雪, 耿明慧. 含哌嗪基团锌离子探针的双光子吸收增强机理[J]. 化学学报, 2023, 81(10): 1371-1378.

Ke Zhao, Xiayu Cheng, Xuexue Ma, Minghui Geng. Mechanism of Two-photon Absorption Enhancement for a Piperazine-based Zinc Ion Probe[J]. Acta Chimica Sinica, 2023, 81(10): 1371-1378.

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图/表 12

图1. 双光子荧光探针D的分子结构及其对锌离子的识别作用

Figure 1. Chemical structure of the two-photon fluorescent probe D and its recognition for Zn2＋

图2. 探针结构变化示意图

Figure 2. Schematic diagram for structural changes of the probe

图3. MD模拟中出现的两种Zn2＋配位模式. (a)模式1: 单配位, (b)模式2: 双配位

Figure 3. Two coordination modes of Zn2＋ which formed in MD simulations. (a) Mode1: mono-coordinated mode, (b) Mode2: bi-coordinated mode

图4. MD模拟中, Zn2＋与相邻N原子间距离的演化. (a)模式1, (b)模式2

Figure 4. Evolution of the distance between Zn2＋ and adjacent N atoms during MD simulations. (a) Mode 1, (b) Mode 2

图5. MD模拟中, 探针、模式1和模式2构型二面角θ (a)和? (b)的统计分布

Figure 5. Distribution of the dihedral angle θ (a) and ? (b) for the configurations of probe, Mode1 and Mode2 during MD simulations

图6. 探针的优化结构(D1, D2)和相应的模式1的优化结构(DZn1, DZn2, DZn3)以及模式2的优化结构(DZn4, DZn5, DZn6)

Figure 6. The optimized geometries of the probe (D1, D2), and the corresponding coordination geometries of Mode1 (DZn1, DZn2, DZn3) and Mode2 (DZn4, DZn5, DZn6)

分子	λ/nm	σ/GM	分子	λ/nm	σ/GM	分子	λ/nm	σ/GM
D1	790	444	DZn1	785	428	DZn4	763	360
D2	793	469	DZn2	788	537	DZn5	805	471
			DZn3	814	572	DZn6	783	438

表1. TPA波长λ和截面σ

Table 1. TPA wavelengths λ and cross sections σ

分子	μ₀₁	μ₀	μ₁	∆μ	α/(°)	ω	δ_2SM
D1	3.401	1.591	7.013	5.577	2.01	0.119	81700 (57900)
D2	3.422	1.935	7.159	5.732	2.25	0.118	88100 (62200)
DZn1	3.414	5.189	8.269	5.542	1.97	0.119	80900 (55800)
DZn2	3.767	5.587	9.940	5.729	2.74	0.119	105000(70000)
DZn3	3.501	4.784	8.341	6.403	0.56	0.114	122800(81200)
DZn4	3.365	6.518	8.398	5.302	2.06	0.122	68700 (44700)
DZn5	3.517	6.436	9.813	5.684	1.43	0.116	95800 (64600)
DZn6	3.440	5.791	7.635	5.720	1.40	0.118	88900 (58100)

表2. 两态模型分析参数, 括号内数值为采用响应理论方法计算的TPA截面(单位: a.u.)

Table 2. Two-state model analysis parameters, the numbers in parenthesis refer to the TPA cross sections from response theory calculations (unit: a.u.)

图7. 分子基态和第一激发态电子密度差等值面图. 绿色和蓝色分别表示电子密度增加和减少. 图中数值为电荷转移距离(单位: nm)

Figure 7. Contour map of the electron density difference between the ground state and the first excited state. Green and blue indicate an increase and decrease in the electron density. The numbers are the charge transfer distances (unit: nm)

图8. TPA截面相对于波长的分布

Figure 8. TPA cross sections are plotted with respect to their excitation wavelengths

图9. 平均TPA谱. 所有结构取自MD模拟, 每个谱是51个结构的平均谱

Figure 9. The averaged TPA spectra. The geometries used in these calculations are taken from the MD. Each spectrum is an average for 51 geometries

图10. TPA截面相对于二面角θ 的分布

Figure 10. TPA cross sections are plotted with respect to the dihedral angle θ

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