A novel pyrazoline-based turn-on ﬂuorescent probe for highly sensitive detection of Al3+ in aqueous solution and its applications

doi:10.21203/rs.3.rs-3234250/v1

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A novel pyrazoline-based turn-on ﬂuorescent probe for highly sensitive detection of Al3+ in aqueous solution and its applications

https://doi.org/10.21203/rs.3.rs-3234250/v1

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published 27 Nov, 2023

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A new efficient fluorescent sensor (E)-3-(1-acetyl-5-styryl-4,5-dihydro-1H -pyrazol-3-yl)-4-hydroxy-6-methyl-2H-pyran-2-one (DRS) for Al³⁺ detection was developed, and the optical properties of DRS were measured in H2O/DMSO (pH = 5.5, 99:1, V/V) solution. DRS showed notable fluorescence enhancement in the presence of Al³⁺ and had good selectivity and sensitivity to Al³⁺. Compared to the probes designed by other previous research groups, a lower detection limit (9.13×10^-9M) and a shorter response time (14 s) were found. Furthermore, the Job’s plot showed that the stoichiometric ratio among DRS and Al³⁺ was 1:1, and 1H NMR, IR and DFT calculations showed that the sensing mechanism of the probe DRS for detecting Al³⁺ was chelation-enhanced fluorescence (CHEF). DRS has also been applied to Al³⁺ detection in actual water samples, drugs, and HeLa cells, indicating that it has potential application value in the biological process of detecting Al³⁺ ion.

Fluorescent probe

Pyrazoline derivatives

Al3+ detection

Chelation-enhanced fluorescence (CHEF)

Al is the third largest component of the earth's crust. But it is not a necessary element to maintain a normal life system and even inhibits the role of other necessary elements in various biological processes (Wang et al. 2010). However, with the advantages of thermal conductivity, high strength, good plasticity, corrosion resistance, and excellent electrical conductivity, aluminum has become very active in specific areas such as food additives, water purification, pharmaceuticals, automobile manufacturing, aerospace industry and energy storage equipment (Gui et al. 2015; Irimia-Vladu 2014; Krupińska 2020; Na et al. 2014; Wilmot et al. 2004; Roy 2021; Ciardelli and Ranieri 2001; Bondy 2010). As a result of the widespread use of Al, the amount of Al³⁺ in the environment enhances. Aluminum is a familiar neurotoxin that can not only lead to various neurodegenerative and neurological disorders (Wang et al. 2010; Walton 2006.) but also hamper plant growth (Cronan et al. 1986; Barcelo and Poschenrieder 2002; Tiwari et al. 2013). At the same time, the Al³⁺ consumption limit is 7 mg per week per kg body weight given by the World Health Organization (WHO) (González-Weller et al. 2010). Therefore, it is necessary to design a kind uncomplicated, quick and reliable sensor for detecting Al³⁺ (Aydin et al. 2020; Singh et al. 2021; Kan et al. 2021; Wei et al. 2020; Roy et al. 2019).

Owing to biological and environmental interests, the identification of metallic ions by the fluorescent probes is gaining more and more attention in the field of chemosensors and molecular imaging. Electron-rich hetero atoms as donors are easy to bind metal ions through chelation, so O atom and N atom are often introduced into fluorophore (Nagarajan et al. 2021; Alici and Erdemir 2015). Pyrazoline, known as dihydropyridine, is a well-known five-membered heterocyclic compound possessed of three carbon atoms and two adjacent nitrogen atom (Matiadis and Sagnou 2020; Knorr 1883; Faisal et al. 2019). Due to the good fluorescence properties and excellent non-toxic bioactivity, a large number of probes have been designed using pyrazoline skeleton as fluorophore for detecting metal ions and molecular imaging (Rangasamy and Palaninathan 2019; Zhang et al. 2021; Bozkurt and Gul 2020; Yang et al. 2021). Pyrazoline derivatives are typical intra-molecular charge transfer compounds. The charge transfer is from the N1 donor to the -C3 = N2 acceptor, which is a conjugate charge transfer (Bai et al. 2007; Wang et al. 2013; Varghese et al. 2017). So, many probes have been developed by changing the substituents in N1 and C3. In fact, there is also a non-conjugate charge transfer of N1 to C5. The substituent in C5 as a electron-donating group enhances the electron donating ability of N1(Song et al. 2009).

In our previous study (Shang et al. 2022), we constructed two probes with pyrazoline and dehydroacetic acid (DHA), in which DHA is covalently attached to pyrazoline in C3. They detected Al³⁺ in H₂O/DMSO (99:1, V/V) solution with 7.50 ×10^− 9 M, 1.76 × 10^− 8 M limit of detection values and about 10 s response times, which are better than other reported results. To further prove whether the conjugate structure in C5 affects fluorescence properties, we introduced a double bond between the phenyl and pyrazoline ring in C5 which may adjust the optical properties of pyrazoline by intramolecular charge transfer (ICT) (Song et al. 2009). As shown in Scheme 1, the probe DRS was synthesized by a simple two-step reaction, and the electron-rich nitrogen and oxygen atoms in the probe structure bind strong Lewis acid Al³⁺. As expected, the probe DRS had good selectivity and sensitivity to Al³⁺, and the detection limit and response time are similar to our previous work. Furthermore, the fluorescence intensity of DRS towards Al³⁺ was stronger than those of the previous two probes in the same conditions. In addition, we also successfully applied DRS to the detection of Al³⁺ in actual samples.

All the reagents in this research were obtained from commercial sources and were not purified. The instruments and experimental methods used in this study are located in the supporting information..

Synthesis of target probe DRS

The probe was synthesized by an unsophisticated two-step reaction as the reported method (Scheme 1) (Saidoun et al. 2018; Swarnkar et al. 2020). Firstly, the Clayson-Schmidt type with dehydroacetic acid and cinnamaldehyde is legally condensed and compound 1 is easily synthesized. Then, compound 1 reacted with hydrazine hydrate through the addition and cyclization process to produce DRS. The synthetic steps of the compound and the characterizations of each substance after synthesis were shown in the support information.

It is worth mentioning that we found that the NMR peaks of DRS changed in different solvents (Fig. 1). For example, when the peak position of the probe DRS in CDCl₃ was 12.74 ppm, it corresponds to the C12-linked -OH on the DHA ring, but the signal disappeared in DMSO-d₆-D₂O; The peak position of olefin proton H¹⁰ in CDCl₃ was 6.03 ppm, while it moved to 6.31 ppm in DMSO-d₆-D₂O; The peak positions of H⁸, H^9b and H^9a in CDCl₃ were 5.19 ppm, 3.75 ppm and 3.62 ppm, respectively; while in DMSO-d₆-D₂O they moved to 5.10 ppm, 3.67 ppm and 3.29 ppm, respectively, indicating that the positions of pyrazoline proton H⁸, H^9b and H^9a shifted up field in DMSO-d₆-D₂O. These results indicated that DRS formed an isomer in H₂O/DMSO (99:1, V/V) solution.

Photophysical properties of free DRS

In the study of sensing characteristics, the absorption spectrum of probe is an important photophysical property. The absorption properties of DRS in H₂O/DMSO (99:1, V/V) solution have been studied by UV-visible spectroscopy. The free DRS has two main absorption bands at 247 nm and 328 nm, respectively, it was speculated that this might be caused by the n-π* transition of the N atom electron pair on the pyrazoline derivative ring ( Yang et al. 2021; Bai et al. 2007). DRS has a very weak emission at 416 nm when excited at 340 nm, which is consistent with the reported results of pyrazoline derivatives (Fig. 2) (Rangasamy and Palaninathan 2019; Bozkurt and Gul 2020; Yang et al. 2021;Bai et al. 2007; Matiadis et al. 2021; Yang et al. 2018; Zhang et al. 2018).

Study on pH

Fluorescent properties are frequently disturbed by pH in the practical application. First, we investigated the pH effects on emission intensity of DRS solution with or without Al³⁺, using HCl and NaOH solutions to adjust pH. As shown in Fig. 3, the fluorescent emission intensity of free DRS was almost unchanged in the pH = 2 ~ 13 range, while adding Al³⁺, the fluorescence intensity of DRS solution increased from 4 to 6 of the pH. In pH = 2 ~ 3, DRS had a weak chelation ability due to the protonation of N2 in pyrazoline ring, whereas the degree of protonation decreases with the increase of pH. So DRS gradually coordinated with Al³⁺, resulting in an increased fluorescence intensity. However, in an aqueous solution of pH = 7, according to the K_a value of Al³⁺ (1.0×10^− 5) and the K_sp of Al(OH)₃ (1.3×10^–33) (Wang et al. 2017), the maximum probable concentration of Al³⁺ is found to be about 1.3×10^-12M, which was insufficient to form a DRS-Al³⁺ complex. Meanwhile, under alkaline conditions, Al³⁺ reacts with OH^- to form Al(OH)₃ precipitate, which reduces the concentration of free Al³⁺. Thus, the optimal pH range of DRS detecting Al³⁺ is 4.0 ~ 6.0. In our experiments, 50 µM Al³⁺ aqueous solution caused a pH = 5.5 system.

Study on properties of Al³⁺ detection by DRS

The UV-vis spectroscopy of DRS (50 µM) had the highest absorption value at around 328 nm (Fig. 4A). When Al³⁺ was gradually added, the absorption peak gradually shifted from 328 nm to 335 nm, and there was an isoabsorptive point near 329 nm, indicating that the complexation between DRS and Al³⁺ was formed. In the fluorescent spectroscopy, when increased the concentration of Al³⁺, the intensity of fluorescent emissions at 416 nm increased progressively (Fig. 4B). There was a good correlation (R² = 0.99145) between fluorescence intensity and Al³⁺ concentration of 0–32 µM range (Fig. 4C), and based on the 3σ/k equation, the detection limit of DRS to Al³⁺ is 9.13×10^− 9M, which was lower than those previously reported for chemical sensors (Table 1) and the WHO limit (7.41 µM) for Al³⁺ in drinking water. It indicated that DRS is sensitive towards Al³⁺ ion.

In practical applications, the rapid detecting test is an important parameter for fluorescent probes. So we investigated the response time of DRS to Al³⁺. It can be seen from Fig. 4D, after adding Al³⁺ to 10 µM DRS solution, the fluorescence emission intensity of the probe DRS increased rapidly, which reached a plateau in about 14 s, and then the intensity value remained almost unchanged for more than 3 min. This may be explained that the combination of DRS with Al³⁺ raised molecule stiffness thus leading to a chelation-enhanced fluorescence (CHEF) pathway (Jeong and Yoon 2012; Goswami et al. 2013). Based on the above results, it was shown that DRS is a potential sensor for real-time monitoring of Al³⁺.

Figure 4A) The absorption spectra of DRS with increasing concentration of Al³⁺ (0–1.2 equiv.); B) Fluorescence emission spectra of DRS with increasing concentration of Al³⁺ (0–32 µM); C) The concentration dependence of DRS and Al³⁺(0–32 µM) at 416 nm based on the 3σ/k equation; D) The time-dependent fluorescence response of DRS (10.0 µМ) to Al³⁺ (50.0 µM). Conditions: H2O/DMSO (99:1, V/V) solution; λex = 340nm and λem = 416 nm.

Selectivity and Competition towards Al³⁺ by DRS

To verify the selectivity of DRS toward Al³⁺ ion, we studied the response of DRS with different metal nitrates (Na⁺, K⁺, Ca²⁺, Mg²⁺, Ba²⁺, Mn²⁺, Zn²⁺, Al³⁺, Cr³⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Cd²⁺, Pb²⁺, Hg²⁺) in H₂O/DMSO (99:1, V/V) solution. As depicted in Fig. 5A and Fig. S4, compared with Al³⁺, the fluorescent intensities of probe DRS with other metal cations were negligible, and the color changes were observed through the naked eye, indicating that DRS has high selectivity for Al³⁺ ion.

To further investigate whether there is any interference with co-existing metal cations, competition experiments were carried out. It can be seen that the fluorescence enhancement of DRS with Al³⁺ ion was not significantly affected in the presence of other metal ions (Fig. 5B), indicating that the probe DRS can probably detect Al³⁺ ion without interaction with other metal ions.

Reversibility experiment

The reversible property of fluorescent probes is one of the important criteria that was desired. So, the reversibility of DRS with Al³⁺ was investigated using EDTA (Fig. 6 and Fig. S5). The fluorescence intensity of free DRS is very weak. After adding Al³⁺ ion into the DRS solution, the fluorescence intensity at 416 nm markedly enhanced, and then adding the same amount of EDTA, the fluorescence intensity decreased. The Al³⁺ and EDTA fluorescent signal conversions cycled at least four times, and the on-off-on fluorescence response was also observed, indicating that DRS can be recycled to detect Al³⁺.

Binding affinity of DRS towards Al³⁺

For the sake of knowing the combination mechanism of DRS with Al³⁺ ions, we determined the stoichiometry of their combination by Job's plot experiment (Fig. 7). When the molar fraction was at around 0.5, the emission intensity of the DRS-Al³⁺ complex reached the maximum, indicating that the stoichiometric combination ratio among DRS and Al³⁺ was 1:1(Saravanan et al. 2020; Singh et al. 2022; Fan et al. 2022). Additionally, the binding constant of DRS to Al³⁺ was calculated to be 2.4×10⁴ M^-1 according to the Benesi-Hildebrand correction equation, showing there was strong cooperation among the probe DRS and Al³⁺, and the formed complex was relatively stable.

To accurately understand the combination of DRS and Al³⁺, we performed FT-IR spectroscopy of the probe DRS and the complex DRS - Al³⁺, respectively (Fig. S6). The peak of asymmetric stretching of the hydroxyl group did not change significantly for the free DRS (3415 cm^− 1) and DRS-Al³⁺ complex (3412 cm^− 1), indicating that hydroxyl group (-OH) of DHA moiety is not the binding site of DRS to Al³⁺.

Furthermore, the peaks of C = O of acetyl and DHA groups for free DRS at 1722 cm^− 1 and 1665 cm^− 1 shifted to about 1637 cm^− 1 when formed DRS-Al³⁺, and the feature peak of C = N on the pyrazoline ring shifted from 1579 cm^− 1 to 1566 cm^− 1. All these results demonstrated that the sites of DRS binding with Al³⁺ may be the carbonyl-O at N1 and DHA, and imine nitrogen on the pyrazoline ring.

In addition, the interaction between the probe DRS and the Al³⁺ was verified through the ¹H NMR titration trial. With the increase of Al³⁺, the protons (H⁸, H⁹, H¹⁰) of the probe DRS moved to the low field shifted obviously (Fig. 9). This may be attributed that the combination of the probe DRS with Al³⁺ enhanced the electron-withdrawing property of carbonyl oxygen and imine nitrogen, resulting into decreases in electron density in some regions and some low-field displacements. The results clearly showed that DRS is bound to Al³⁺ by N2, and carbonyl-O of acetyl at N1 and ester of DHA.According to the above results of experiments and literature (Wang et al. 2022; Das et al. 2022; Zhao et al. 2022; Anu et al. 2021), we proposed a possible sensing mechanism for DRS detecting Al³⁺ ions (Scheme 2). The complexation of the probe DRS with Al³⁺ increased the rigidity of the molecule, thus leading to chelation fluorescence enhancement (CHEF).

Theoretical calculation of DRS-Al³⁺ complex

To verify the feasibility of the proposed binding mechanism, a density functional theory (DFT) theoretical calculation was employed to optimize the structures of the DRS and DRS-Al³⁺ complexes and explore the HOMO and LUMO states using Gaussian 09 program by the B3LYP/6-31G (+, d, p) method. The optimized structures of DRS and two probable DRS-Al³⁺ complexes were shown in Fig. 10. The optimized structure of DRS showed that the DHA ring and pyrazoline ring are not coplanar, whereas for DRS-Al³⁺ complex, DHA and pyrazoline rings are in the same plane leading to the molecule rigidity increasing. Meanwhile, it is evident that the electron density of carbonyl O (-0.510 eV) is more than that of hydroxyl oxygen (-0.469 eV) in the optimized structure of DRS, and the bond distance (Å) of O-Al in DRS-Al³⁺-1(1.773) is shorter than that of DRS-Al³⁺-2 (2.083), suggesting that DRS-Al³⁺-1 is the formation of DRS-Al³⁺ complex. Thus, the binding sites are pyrazoline C = N, acetyl C = O and DHA C = O.

As can be seen from Fig. 11, for DRS, the electron distributions of HOMO and LUMO were located on DHA and pyrazoline rings with a HOMO-LUMO energy gap of 3.928 eV. For the DRS-Al³⁺ complex, both HOMO and LUMO energy levels were significantly stabilized as compared to free DRS, and the HOMO and LUMO energy gap reduced drastically to 0.671eV which not only indicated the generation of a stable complex but also led to a red shift in the absorption agreed well with the UV–vis spectra.

Actual Samples Study

According to the good fluorescence performance of the probe DRS, we further expanded the possibility of application in actual water samples, drugs, and test papers. Firstly, the practicality of DRS was evaluated by test strips. We dipped the filter paper into DRS (50 µM) solution, and then dried it in the air to get test strips. Subsequently, the aqueous solution of 100 µM various metal ions was added to the test strips. It was found that only the test strip impregnated with Al³⁺ showed bright blue fluorescence under ultraviolet light (λ = 365 nm) (Fig. S7).

Furthermore, the fluorescence intensity and recovery of the probe in three water samples (ultrapure water, tap water and Yellow River water) were assayed. It can be seen that there were good linear relationships between the fluorescence intensity and the concentration of Al³⁺ in water samples, and the recovery rates were about 90% (Fig. 11 and Table S1). We further used DRS to detect Al³⁺ in two anti-acid tablets containing Al³⁺ (talcid and gastropine). The Al³⁺ containing sample solution from drugs used in this test was obtained by the previous method (Shang et al. 2022). When the sample solution was added to 10 µM DRS solution, the maximum peak appeared at 416 nm with a visible color change from colorless to bright blue under ultraviolet light (λ = 365 nm) (Fig. 12). These results showed that DRS can be used for fluorescence monitoring of Al³⁺ in drug samples.

Imaging applications

To gain insight into the applicability of DRS in biology, the detection of exogenous Al³⁺ in HeLa cells was performed. First, the cytotoxicity of DRS was assayed by the MTT method (Fig. 13A). The results showed that cell viability is greater than 85% when the cells were treated with the DRS concentrations of 0, 5, 10, 20, 30, 40, and 60 µM for 12 h, indicating that the probe DRS could be available in the biological field.

In imaging studies, when using the probe DRS (10 µM) solution incubated HeLa cells for 30 min, faint blue fluorescence was observed (Fig. 13B), indicating that the probe DRS migrated into the cells and assembled, and the endogenous Al³⁺ ion in the HeLa cells was more than nano-molar. After adding 50 µM Al³⁺ to the cells and incubating for another 30 min, the fluorescence was significantly enhanced. These results showed that the probe DRS was well permeable to the cell membrane and can be used for the detection of Al³⁺ in cells.

In general, we successfully synthesized a pyrazoline-based fluorescent sensor DRS. The selectivity and sensitivity of probe DRS to Al³⁺ were superior to other competing metal ions, and the limit of detection was lower than the limiting value of Al³⁺ in potable water of the World Health Organization (WHO). The possible binding mode of the probe DRS and Al³⁺ were explored through Job's plot curved line, ¹H NMR, IR and DFT computation. The experiment results explained that the detection mechanism of probe DRS for Al³⁺ is the chelating fluorescence enhancement (CHEF) effect. The detection of Al³⁺ in actual water and drug samples provided the foundation for the real application of probe DRS. Moreover, the probe DRS has been successfully used for fluorescence imaging to detecting Al³⁺ in living cells.

Acknowledgements. This work was supported by Tianyou innovation team of Lanzhou Jiaotong University (TY202004).

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Supplementary data

Electronic Supplementary Material associated with this article can be found in the online version of this paper (DOI: xxxxxxxxxx).

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Table 1 is available in Supplementary Files section.

Schemes are available in Supplementary Files section.

Checklist.xls
GraphicalAbstractYJShang.docx
SupportinginformationYJShang.docx
Scheme1.png
Scheme 1. Synthesis of target probe DRS.
Scheme2.png
Scheme 2. Possible binding mode of DRS toward Al³⁺.
Table1.docx

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You are reading this latest preprint version

A novel pyrazoline-based turn-on ﬂuorescent probe for highly sensitive detection of Al3+ in aqueous solution and its applications

Status:

Journal Publication

Version 1

Abstract

Figures

Introduction

Experimental

Results and discussion

Synthesis of target probe DRS

Photophysical properties of free DRS

Study on pH

Study on properties of Al³⁺ detection by DRS

Selectivity and Competition towards Al³⁺ by DRS

Reversibility experiment

Binding affinity of DRS towards Al³⁺

Theoretical calculation of DRS-Al³⁺ complex

Actual Samples Study

Imaging applications

Conclusions

Declarations

References

Table 1

Schemes

Supplementary Files

Status:

Journal Publication

Version 1

A novel pyrazoline-based turn-on ﬂuorescent probe for highly sensitive detection of Al3+ in aqueous solution and its applications

Status:

Journal Publication

Version 1

Abstract

Figures

Introduction

Experimental

Results and discussion

Synthesis of target probe DRS

Photophysical properties of free DRS

Study on pH

Study on properties of Al3+ detection by DRS

Selectivity and Competition towards Al3+ by DRS

Reversibility experiment

Binding affinity of DRS towards Al3+

Theoretical calculation of DRS-Al3+ complex

Actual Samples Study

Imaging applications

Conclusions

Declarations

References

Table 1

Schemes

Supplementary Files

Status:

Journal Publication

Version 1

Study on properties of Al³⁺ detection by DRS

Selectivity and Competition towards Al³⁺ by DRS

Binding affinity of DRS towards Al³⁺

Theoretical calculation of DRS-Al³⁺ complex