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A Single-Fluorophore Multicolor Molecular Sensor That Visually Identifies Organic Anions Including Phosphates

2023; Chinese Chemical Society; Volume: 6; Issue: 3 Linguagem: Inglês

10.31635/ccschem.023.202302900

2096-5745

Zezhou Zong, Qi Zhang, Da‐Hui Qu,

Analytical Chemistry and Sensors

Open AccessCCS ChemistryRESEARCH ARTICLES1 Mar 2024A Single-Fluorophore Multicolor Molecular Sensor That Visually Identifies Organic Anions Including Phosphates Zezhou Zong, Qi Zhang and Da-Hui Qu Zezhou Zong Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 , Qi Zhang *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 and Da-Hui Qu *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 https://doi.org/10.31635/ccschem.023.202302900 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Developing fluorescent sensors for small-molecule phosphates offers opportunities in optically detecting biorelevant reactions and events. However, it remains elusive how to identify phosphates from other anions, such as carboxylates and sulfates, because current synthetic phosphate receptors lack selectivity. Here we report the construction of a multicolor fluorescent sensor that can identify phosphates from other analogous anions. The key design principle is to take advantage of the highly sensitive conformation-dependent emissive wavelength of diphenyl-9,14-dihydrodibenzo[a,c]phenazine fluorophores to sense the minor structural differences between phosphates and other anions, for example, sulfates and carboxylates. The effect of structural factors such as spacer length and urea versus thiourea has been investigated by comparing the optical properties and binding affinities with the phosphate receptors. This strategy provides a simple and robust fluorescent sensing solution to optically analyze small-molecule phosphates with anti-interference performance. Download figure Download PowerPoint Introduction Fluorescent sensing anions with artificial receptors provide an important solution for optically detecting anionic molecules of interests in biological or environmental research.1,2 Methodologies have been well established in the past decades on the fluorescent detection of various anions,3 including chloride,4 fluoride,5 carboxylates,6,7 and so on. Among them, organic phosphates are a family of biologically relevant anions that widely exist in many biomolecules and are involved in numerous bioreactions, which has driven the increasing research interest in exploiting fluorescent sensors of phosphates.8 The general design strategy is to couple a fluorophore with a phosphate recognition site to allow fluorescent changes after molecular recognition.9,10 With the development of artificial receptors11–13 and in-depth research of host–guest luminescent systems,14–20 several sensing mechanisms have been established, such as photoinduced electron transfer,21 Förster resonance energy transfer,22 photoinduced charge transfer (PCT),23–25 and aggregation-induced emission,26 resulting in a few successful examples of on–off sensors.27–30 However, one of the common challenges of these strategies is difficulties in the selective detection and identification of different anions, which inherently originates from the similar molecular recognition mechanism of these anions. Therefore, it is essential but also challenging to achieve sensitive fluorescent sensors, ideally capable of direct visualization by multicolor emission, that identify different anions including phosphates. Vibration-induced emission (VIE), coined by Tian and Chou et al. to describe the unique fluorescent properties of diphenyl-9,14-dihydrodibenzo[a,c]phenazine (DPAC),31–33 has aroused extensive attention in the design of smart fluorescent systems and materials.7,34–38 The key feature of this structurally concise fluorophore is its ability to simultaneously emit multicolor molecular fluorescence from the fused ring, in which the emission wavelength is very sensitive to the conformational freedom of the two symmetric phenyl groups. Our previous studies have disclosed a robust strategy to molecularly engineer the size and rigidity of the spacer that intramolecularly cyclizes the two phenyl groups, achieving a single-fluorophore-based molecular system with multicolor emission.39 Based on these studies, we hypothesize that this intramolecularly cyclization strategy can be expanded to the recognition and detection of phosphate, which might amplify the minor structural difference of phosphates and other anions and enable visualizable fluorescent sensors. Here we report the successful fluorescent multicolor sensing of organic phosphates by a VIE-based fluorophore (Figure 1). The molecular design is based on the immobilization of two "arms" as flexible recognition sites for phosphates, taking advantage of the strong binding affinity of urea units as strong hydrogen bond donors. The V-shape molecular conformation of DPAC units further facilitates the simultaneous noncovalent capture of phosphate guests to enhance the binding affinities through a synergistic effect. The key feature of this molecular system rests on the very subtle interplay between DPAC vibrational freedom and the type of captured guest anions, allowing guest-dependent multicolor fluorescent output and direct visual identification. We anticipate that this example would be a model for combining VIE with fluorescent sensors and would be push to the substantial development of phosphate sensors. Figure 1 | Conceptual illustration of the DPAC-based fluorescent sensors for different organic anions. Download figure Download PowerPoint Experimental Methods All reagents were used as received unless otherwise stated. All solvents were reagent grade and were dried and distilled prior to use according to standard procedures. All deuterated solvents were purchased from the company Cambridge Isotope Laboratories (United States). Flash column chromatography was performed using silica gel (Greagent, 200–300 mesh) to purify crude products. The 1H and 13C NMR spectra were measured on a Brüker AV-400 and AV-600 spectrometer (Brüker, Switzerland) at 298 K. The electrospray ionization mass spectrometry was obtained on an LCT Premier XE mass spectrometer (Waters, United States). The UV-Vis absorption spectra data were documented by a Shimadzu UV-2600 UV-Vis spectrophotometer (Shimadzu, Japan), and fluorescent spectra were acquired by a Shimadzu RF6000 spectrofluorophotometer (Shimadzu, Japan). Reverse-phase high-performance liquid chromatography purification was performed on a Shimadzu CBM-20A instrument with Shim-pack GIST (Shimadzu, Japan) C18 5μm (20 × 250 mm preparative) column. More experimental details and characterization of products are available in the Supporting Information. Results and Discussion The molecular design is based on the molecular engineering modification of the two "arms" of the DPAC fluorophore (Figure 1). The fundamental principle is to correlate the supramolecular recognition with the conformational freedom of the photo-excited vibration motion of DPAC, which led us to investigate the structure–emission relationship in terms of the effect of spacer length (determined by the numbers of methylene linkages, i.e., n) as well as the hydrogen bond donors (i.e., urea or thiourea units). Starting from the diformyl-DPAC, the formation of imine followed by reduction yielded the bis-secondary-amine intermediate (Scheme 1), which was then substituted to produce the phthalimide precursors with different linkers (n = 2–4). Subsequent hydrazinolysis of imides and thiourea/urea generation reaction resulted in six different DPAC receptors 1– 6 (Figure 1), whose molecular structures were fully characterized by 1H and 13C NMR spectroscopy and high-resolution mass spectroscopy (see the Supporting Information for more details). Scheme 1 | Synthesis of the receptor 1. Download figure Download PowerPoint We first investigated the photophysical properties of DPAC receptor 1 with four methylenes as the spacer and thiourea as the binding sites. The receptor 1 showed a distinctive orange emission (λm = 600 nm in acetone, Supporting Information Figure S1) in polar solvents as a characteristic property of DPAC fluorophore with high conformational freedom. Upon dissolving in apolar solvents, the intensity of the emissive band at 442 nm increased ( Supporting Information Figure S1), suggesting a decreased conformational freedom due to the confinement of H bonds. This blue emissive band became more predominant when diluting the solution, as indicated by the concentration-dependent fluorescent spectra in CH2Cl2 ( Supporting Information Figure S2–S5), which suggested intramolecular hydrogen bonds were responsible for the observed fluorescent blueshift. This very subtle dependency on solvents and concentrations showed the highly sensitive emissive properties of this dynamic fluorophore under different conformational freedom. The binding properties of receptor 1 for oxoanions were initially investigated by titrating receptor 1 with monobasic phenylphosphonate anion (PhPO3H−) as its tetrabutylammonium salt in acetone. With increasing amounts of PhPO3H−, the fluorescence of the mixture underwent a remarkable transition from orange-red to nearly white emission. The appearance of a new emissive band at 483 nm accompanies the decrease of the band at 600 nm (Figure 2a), resulting in a clear isosbestic point at 596 nm in the fluorescent spectra. The change of the two fluorescent bands plateaus after the addition of 3.0 equiv of PhPO3H−. The fluorescent color coordinates were calculated and plotted in a Commission Internationale de l'Eclairage (CIE) 1931 chromaticity diagram (Figure 2b). The coordinates change from orange-red (0.43, 0.36) to near white (0.31, 0.34) to the final state (0.27, 0.33). Meanwhile, phosphates PhPO3H− and PhPO32− were compared (see titration experiments and details in Supporting Information Figure S6); they show similar fluorescent titration curves, which hint that hydrogen bonds are the predominant factor contributing to the supramolecular host–guest recognition. Figure 2 | (a) Fluorescent titration experiment by adding increasing amounts of PhPO3H− to the solution of 1 (λex = 360 nm, [1] = 10 μM; solvent, acetone). (b) CIE 1931 chromaticity diagram and inset digital photographs showing the color change of solutions of 1 containing various amount of PhPO3H− from initial orange to near white (0.8 equiv; CIE 1931: (0.31, 0.34)). (c) Least-squares nonlinear fitting of the normalized change in fluorescence at 484 nm obtained as a function of concentration on the basis of the fluorescence titration of 1 with PhPO3H− ([1] = 10 μM; solvent, acetone). Inset: Job plot analysis corresponding to the formation complex between 1 and PhPO3H−. The total concentration of 1 and PhPO3H− was held constant at 3.0 × 10−5 M. (d) CIE 1931 chromaticity diagram and inset digital photographs showing the different color of the solution of 1 adding various oxoanions (PhPO3H−, PhSO3−, PhCO2−). Download figure Download PowerPoint To further understand the binding features of 1 with PhPO3H−, the binding stoichiometry was determined by a fluorescent Job's plot. The plot showed a maximum at the 0.5 mole fraction of 1, indicating a 1:1 complex of 1 and PhPO3H− (Figure 2c). By fluorescence spectral titration curve fitting, the binding constant (K1:1) was determined as (4.3 ± 0.6) × 105 M−1, indicating the strong binding of 1 and PhPO3H−. With linear correlation of the emission intensity ratio I483/I600 with the PhPO3H− concentration over the 0–1 μM range, the limit of detection was also determined as 94.4 nM ( Supporting Information Figure S7). Compared with the binding of 1 and phosphates in acetone, the receptor showed comparable responsiveness in CH3CN and tetrahydrofuran, but relatively low sensitivity in dimethylformamide and dimethyl sulfoxide ( Supporting Information Figures S8-11), probably due to the competition effect from the high solvation ability of the highly polar solvents. As a comparison, fluorescent spectroscopic titrations with benzoate (PhCO2−) and benzenesulfonate (PhSO3−) were also performed. The addition of PhCO2− to receptor 1 resulted in a slight decrease in the emission band at 600 nm and an increase in the new emission band at 482 nm ( Supporting Information Figures S12 and S13). With the addition of PhCO2− in comparison with PhPO3H−, the fluorescent intensity ratio I480/I600 changed less significantly, although the location of the emissive bands was similar. With the addition of PhSO3−, the fluorescent color of the mixture changed from orange to purple. In contrast to the phenomenon above, fluorescent spectra showed that an emissive band at 432 nm increased with titration ( Supporting Information Figure S14). The binding mode of compound 1 and PhCO2−/ PhSO3− was inferred to be a mixture of 1:1 and 1:2. From the fluorescent spectral titration, the high energy band increased with the increasing amount of oxoanion, related to the formation of a 1:1 complex that limits the conformation freedom of DPAC and enhances blue emission. Further addition of oxoanions led to decrease of the blue emission, revealing the transition from a 1:1 to 1:2 complex, that the 1:2 complex may have more degrees of freedom. The CIE chromaticity diagram demonstrates that the fluorescence response of 1 on ligand binding varied with different oxoanions, with yellow green (0.27, 0.33) for PhPO3H−, orange-yellow (0.37, 0.37) for PhCO2−, and purple (0.26, 0.20) for PhSO3−, meaning the directly visual discrimination of these structurally similar oxoanions (Figure 2d). 1H NMR-based titration experiments were carried out to explore the details of binding. The 1H NMR spectra of 1 with increasing amounts of PhPO3H− are shown in Figure 3 and Supporting Information Figures S15 and S16. The addition of PhPO3H− results in a series of shifts of DPAC (H3 and H9,10), phenylthiourea (H19, H20, and H21), and linker protons (H11, H12, H14, H15, and H16), indicating interaction between binding sites and oxoanions take place. After adding 1 equiv of PhPO3H−, the phenylthiourea protons (H20 and H21) and linker protons (H15 and H16) next to thiourea exhibit an upfield shift, with Δδ = −0.17, −0.21, −0.07, and −0.09 ppm, respectively, attributed to the shielding effect from thiourea–anion binding. Meanwhile, the phenylthiourea proton (H19) exhibits a downfield shift due to the deshielding effect of the oxygen atom of the oxoanions. The protons of H3 and H9,10 protons of DPAC exhibit a shift with Δδ = +0.02 and −0.14 ppm, respectively, which is consistent with previous observations of noncovalently locked DPAC in the ground-state conformation.39 This evidence supports that the anion binding could confine the conformational freedom of DPAC, thus driving the emission change from orange-red to white. Linker protons around the tertiary amine (H11, H12, and H14) exhibit a downfield shift, with Δδ = +0.10, +0.05, and +0.10 ppm, respectively. It has been reported that receptors with a tertiary amine group can be protonated by oxoanions, and the charge–charge interaction between positive-charged receptors and anions stabilizes the complex and increases binding constants.40 The downfield shift is attributed to the deshielding effect from positively charged N atom with the protonation of the tertiary amine group. Assuming a 1:1 binding model in Bindfit, a fit with NMR spectral titration was obtained ( Supporting Information Figure S17) with an association constant of (1.51 ± 0.64) ×105 M−1, which is two orders of magnitude larger than the association constant of 1 and PhSO3−((2.05 ± 0.11) × 103 M−1 Supporting Information Figures S18–S20). The high binding constant between 1 and PhPO3H− indicates that the synergy of multiple hydrogen bond and charge–charge interaction could significantly improve the binding constant of the complex. Figure 3 | 1H NMR spectra of 1 (0.5 mM) in acetone-d6 in the presence of increasing concentrations of phenylphosphonate. The positions of the labelled protons are marked in Scheme 1. Download figure Download PowerPoint We next explored the inner structure–property relationships by molecularly engineering the recognition sites and spacer length. Hence, receptors 2– 6 were designed and synthesized (see detailed procedures and structural characterization in the Supporting Information). Receptors 2– 6 showed orange emission in diluted polar solvent due to the high conformational freedom of the DPAC unit. All receptors were subjected to fluorescent titration of oxoanions with the same conditions except for 6, whose solubility is too poor in acetone to support the titration ( Supporting Information Figures S21–S32). For receptors 2– 5, as the concentration of PhPO3H− increased, the fluorescence showed a blueshift like receptor 1. Titrated with PhPO3H−, fluorescent spectra indicated that the low-energy emission band at 600 nm was quenched, while high-energy emission bands located at 480 nm for 2, 487 nm for 3, 473 nm for 4, and 485nm for 5 intensified (Figure 4a,b and Supporting Information Figures S21–S24). The CIE chromaticity diagram shows receptors 1– 5 possess different fluorescent color at their plateau (Figure 4c). These results jointly confirmed the reliability and generality of this design strategy, that is, using DPAC fluorophore as a functional unit to optically sense the noncovalent host–guest binding events. Figure 4 | (a) Fluorescence emission spectral changes upon the addition of increasing amounts of PhPO3H− to a solution of 2 (λex = 360 nm; [2] = 10 μM; solvent, acetone). (b) Fluorescence emission spectral changes upon the addition of increasing amounts of PhPO3H− to a solution of 3 (λex = 360 nm; [3] = 10 μM; solvent, acetone). (c) CIE 1931 chromaticity diagram and digital photographs (inset) showing different fluorescent color of solutions of PhPO3H− with receptor 1–5. (d) Binding constants for receptor 1–5 and PhPO3H− in acetone at 298 K. Download figure Download PowerPoint An interesting difference in binding affinities was observed when comparing analogous receptors 1– 5. The binding stoichiometry of 2– 5 and PhPO3H− were determined by fluorescent Job's plot, which indicates all were a 1:1 complex. The associated constants of these complexes were fitted with the fluorescent titration data and are shown in Figure 4d and Supporting Information Table S1. From the results, we inferred that both the functional group of binding site and spacer length affected the binding constants. When comparing thiourea and urea derivatives with the same spacer length, the phenylphosphonate binding capacity of receptors with thiourea as their binding sites ( 1 and 3) were stronger than the corresponding urea receptors ( 2 and 4). The difference in binding capacity was attributed to the strength of thiourea and urea as hydrogen bond donors. Generally, a hydrogen bond could be assumed as a "frozen" proton transfer from the donor (acid) to the acceptor (base), in which the more likely the proton transfer, the stronger the H-bond interaction.41 In previous literature, thioureas have lower pKa's in comparison with urea (pKa = 21.1 and 26.9, respectively in DMSO42), which makes thioureas stronger phosphate-binding groups. With the same binding but various spacer length, the PhPO3H− binding ability of receptors ranked as 2 > 4 > 5 and 1 > 3 The spacer-dependent binding ability was attributed to the cavity size and the structural rigidity. As cleft-like receptors, the cavity of receptors 1– 5 were determined by the spacer length. Binding the large oxoanions, the small cavity of the short-spacer receptor was insufficient, and the binding affinity would decrease due to incomplete formation of the designed quadruple hydrogen bond. In contrast, the longer spacer would decrease the structural rigidity of receptor for better hydrogen bonding between binding sites and the tetrahedral phenyl phosphonate. Previous literature43 regarding fluorophore aggregation suggests that the anion-induced blueshifted emission could be caused by the formation of polymer complex with the same stoichiometry. Therefore, we list some evidence that supports the non-aggregated host–guest complex: (1) The sharp and well-split proton signals in 1H NMR spectra (Figure 3) suggest a "molecular dissolution" instead of aggregation; (2) The receptor 1 with longer linkage (higher conformational freedom) and thiourea (lack of intermolecular H bonds) shows the highest binding constant (Figure 4d), revealing a non-aggregated host–guest combination; (3) Fluorescence titration of receptor 1 and PhPO3H− at a lower concentration of receptor 1 ([ 1] = 2 μM Supporting Information Figure S33) shows that dilution does not affect the recognition ability, further excluding the case of aggregation, which is entropically negative in such highly diluted solutions. Conclusion In summary, we have successfully demonstrated how the VIE dynamic fluorophore can enable a "smart" fluorescent sensor that can visually identify different organic anions in solution phase. By engineering the molecular structure, very high binding constants can be achieved up to 105 M−1, allowing a very low limit of detection at the level of 94.4 nM. Due to the wide existence and important role of phosphate anions in biological systems, the direct optical discrimination by a broad wavelength of fluorescent window, using a single fluorophore, provides many opportunities for developing fluorescent imaging techniques as well as molecular sensors for analytic use. We envision that this research will act as a starting point for the color-tunable fluorescent sensing and imaging of biologically relevant phosphates. Supporting Information Supporting Information is available and includes synthetic methods and characterizations, spectroscopic details, and characterization. Conflict of Interest There is no conflict of interest to report. Funding Information This work was supported by the National Natural Science Foundation of China (grant nos. 22220102004 and 22025503), Shanghai Municipal Science and Technology Major Project (grant no. 2018SHZDZX03), the Innovation Program of Shanghai Municipal Education Commission (grant no. 2023ZKZD40), the Fundamental Research Funds for the Central Universities, the Programme of Introducing Talents of Discipline to Universities (grant no. B16017), Science and Technology Commission of Shanghai Municipality (grant no. 21JC1401700), and the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study (grant no. SN-ZJU-SIAS-006). Acknowledgments We thank the Research Center of Analysis and Test of East China University of Science and Technology for help with the characterization. References 1. Guo C.; Sedgwick A. C.; Hirao T.; Sessler J. L.Supramolecular Fluorescent Sensors: An Historical Overview and Update.Coord. Chem. Rev.2021, 427, 213560. 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