Mechanism of Two-photon Absorption Enhancement for a Piperazine-based Zinc Ion Probe

doi:10.6023/A23050248

Abstract

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

Cite this article

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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Fig. & Tab. 12

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

Figure 2. Schematic diagram for structural changes of the probe

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

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

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

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

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)

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

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)

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

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

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

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