Benzene Sulfonyl Linked Tetrasubstituted Thiacalix[4]arene for Selective and Sensitive Fluorometric Sensing of Sulfosulfuron Along with Theoretical Studies

doi:10.21203/rs.3.rs-2437846/v1

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Benzene Sulfonyl Linked Tetrasubstituted Thiacalix[4]arene for Selective and Sensitive Fluorometric Sensing of Sulfosulfuron Along with Theoretical Studies

https://doi.org/10.21203/rs.3.rs-2437846/v1

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published 17 Mar, 2023

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Herein, we designed two fluorescent Tetrasubstituted Benzene sulfonyl appended Thiacalix[4]arene receptors named PK^1–2 which sensitively and selectively detect Sulfosulfuron among other herbicides and pesticides. The detection limit (LOD) was found to be 0.21 ppm and 0.35 ppm, and the Enhancement constant (Ks) was determined 7.07 X 10⁴ M^− 1 and 5.55 X 10⁴ M^− 1 for PK¹ and PK² respectively. Using the Non-linear regression method, the Association constant was obtained as 2.1 X 10⁴ M^− 1 and 2.23 X 10⁴ M^− 1 whereas the binding ratio was found to be 1:1 for both PK^1–2 respectively. Additionally, the interference studies show the selective nature of receptors for Sulfosulfuron among its sulfonylurea family. To further confirm the binding mechanism computational investigation was carried out, which validates the 1:1 binding ratio. The receptors were found to be recyclable in nature with simple Acid-Base treatment. This new approach of using Supramolecules as fluorescent probes for sensitive and selective detection of herbicides are rare in the literature.

Thiacalix[4]arene

“Turn-On” Fluorescent sensor

Pesticide sensing

DFT calculation

Water pollution management has remained a global challenge as the existence of living organisms revolves around water. Anthropogenic activities such as discarding irrigation run-off containing pesticides and industrial wastewater into the water bodies have contributed immensely to the water contamination and hence led to the scarcity of potable drinking water. To meet the upsurge of food demands, the use of pesticides has ramped up globally as they protect various crop-damaging species hence, increasing the yield. Conversely, the extravagant use of these pesticides results in large-scale environmental deterioration affecting the soil, plants, water, edible product, and human beings. Frequent reports show that pesticides have exceedingly lowered the standard of drinking water by making their way to the aquatic system via agricultural runoff. The permissible level of pesticides in drinking water was set at 0.1µg/L by European Union (EU) standards of drinking water. However, various reports reveals the pesticide levels to be found exceeding above the limits set by EU due to their ability to persist in the environment [1–4].

Depending upon the function and requirements of the crops, various pesticides are available in the global market. Amongst the variety of crops, wheat is a widely sought-after crop across the globe owing to its source of nutrients in food; its production is thus of prime importance. In order to boost crop yield and meet global demands, the most widely used herbicide (a class of pesticide ) for wheat production is Sulfosulfuron [5]. It is a widely used sulfonylurea herbicide for the protection of wheat by suppressing the growth of Brome, Phalaris minor, Quack grass (Elymus repens), Grip grass (Galium aparine), broadleaf weeds, wild oats, and apera Spica-venti. It has been found safe on wheat for its application in pre-emergence and post-emergence to weeds [6]. Other than wheat it has also demonstrated efficient selective controlling of weeds in a variety of field crops such as cotton, rapeseed, corn, alfalfa, vegetables like potato and tomato, and orchards including olive groves [7]. Owing to the elevated demand for Sulfosulfuron, its global consumption is estimated to be above USD 91.27 million in 2020-2025. Ultimately, all these pesticides and their residue get accumulated in the environment, causing terrestrial and aquatic pollution and entering the food chain, affecting the ecosystem as a whole. The reports show that Sulfosulfuron possesses acute toxic effects on aquatic organisms [8][9]. Hence, the rapid, reliable, precise, and effortless detection of Sulfosulfuron is a need of the moment.

Several efforts have been made earlier and a considerable amount of work has been done in the detection of pesticides and its residues using different platforms such as macrocycles/supramolecular scaffolds [10–18], MOFs [19–22], polymers [23], nanoparticles [24–26] etc. A variety of techniques such as High-performance liquid chromatography (HPLC), Thin layer chromatography (TLC), Liquid-Liquid Extraction (LLE), Solid Liquid Extraction (SLE), Gas chromatography (GC), Immuno-affinity chromatography Coupled-column capillary Liquid chromatography/Mass spectrometry (IAE/LC/LC/MS/MS) are reported in the literature [27] for the detection of pesticides. However, these methods are time consuming; require cumbersome sample preparation, separation and demands sophisticated instruments and their handling which makes the process tedious and long. Eliminating these hassles, the optical techniques such as UV-Visible and Fluorescence spectroscopy offer sensitive, selective, quick and reliable results and works even in low concentrations, and thus have gained momentum in the last few decades [28] .

Calix[n]arenes (n=4,5,6,8) – the third generation of supramolecules have the electron rich cavities, essential rigid structural design, synthetic tailor-ability, definite conformations, distinct ion-binding site and convenience of derivatization which set them apart from the general organic or inorganic entities and thus makes them fascinating for designing optical sensors. For this reason, Calix[4]arenes scaffold has been widely utilized in the development of molecular sensors, cation/anion sensors, bioimaging, non-linear optical compounds, self-assembly, drug delivery, gels, OLED, in vivo and in vitro imaging and for other biological applications [29]. Moreover, the properties of Calix[4]arenes gets dramatically enhanced by replacing their methyl bridges with Sulphur and hence forming a new class of macrocycles named Thiacalix[4]arenes. The insertion of hetero atom Sulphur can act as an additional coordination site due to the lone pair of electrons on Sulphur and makes further modification easy. Furthermore, they show superior conformational flexibility than the regular Calix[4]arenes and higher complexation ability towards the metal ions or neutral molecules [30][31]. Despite this, the literature on Thiacalix[4]arene based pesticides sensors is scarce and only few reports on sensing pesticides using Thiacalix[4]arene scaffold are available [32,33]. To the best of our knowledge, no fluorescent sensor has been reported in the literature that selectively senses Sulfosulfuron using Fluorescence spectroscopy. Thus, in an endeavor to develop a sensitive and selective sensor for Sulfosulfuron, herein, we report two novel Benzene Sulfonyl appended Thiacalix[4]arene based fluorescence “Turn-on” sensors named PK¹ and PK² which offers sensitive and selective sensing of Sulfosulfuron amongst the other common pesticides in this study.

PK^1-2 were synthesized using Thiacalix[4]arene. In a 100ml RBF (round bottom flask), a heterogenous mixture of Thiacalix[4]arene, Potassium carbonate, and Potassium iodide were taken in Acetonitrile solvent and refluxed for next 1 hour. After the solution cools down, to this 2,4-dimethyl benzene sulfonyl chloride and 4-isopropyl benzene sulphonyl chloride were added slowly and the reaction was refluxed for 24 hours to offer PK¹ and PK² respectively. Synthetic procedure is mentioned briefly in Materials and Methods section. (SI Page No. S4-S6)

(2.1) Photophysical studies:

Selective sensing ability of both receptors PK^1-2 were evaluated using both UV-Visible and Fluorescence spectroscopic studies in the presence of various pesticides in aqueous system. For spectroscopic competitive studies pesticides such as Ametryn, Atrazine, Clodinafop, Chlorsulfuron, Metalaxyl, Pretilachlor, Propanil, Propargyl, Pendimethalin, Simazine, Simetryn, Sulfosulfuron, Tebuconazole, Terbutryn, and Tricyclazole were considered. The stock solution 0.05 mM of both ligands were prepared in ACN:Water system (9:1). The UV-Visible spectra show absorbance maxima at 230 nm and 283 nm for receptor PK¹ and 273 nm for receptor PK² (Figure 02 and SI Figure S13). Significant changes in the UV-Vis spectra (Bathochromic shift) for receptor PK^1-2 were observed only in the presence of Sulfosulfuron, whereas no remarkable changes were observed with other pesticides. Similarly, in the fluorescence spectra, strong emission maxima were observed at 373 nm and 393 nm for receptor PK¹ and at 410 nm and 431 nm for receptor PK², upon excitation at 300 nm and 290 nm for PK^1-2 respectively. For both PK^1-2, a “Turn-ON” fluorescence in the spectra was observed in the presence of Sulfosulfuron. However, no changes were observed for rest of the pesticide (Figure 02 and SI Figure S13). Both UV-visible and Fluorescence titration experiments were carried out to further confirm the selectivity of PK^1-2 with incremental concentration of Sulfosulfuron (0.1 mM - 1.0 mM). Detection limit (LOD) was calculated using the 3σ-method [34] with incremental addition (0.1 mM - 0.4 mM) of Sulfosulfuron (SI Figure S14) and tabulated in Table 01. The quantum yield for PK^1-2 were found out to be 0.061 and 0.113 respectively using tryptophan (quantum yield = 0.14) as standard [35] for the emission spectra of PK^1-2 whereas, for PK^1-2-SS interaction, the quantum yield were determined to be 0.093 and 0.133 respectively. Similarly, Enhancement constant (Ks) [36] were determined for both the ligands (Table 01). A linear fitting suggests that enhancement is due to static mechanism. (SI Figure S14).

Ligand	K_s (M^-1)	LOD	R² (Coefficient)	Standard deviation
PK¹	7.07 X 10⁴	0.21ppm	0.9847	2218.87
PK²	5.55 X 10⁴	0.35ppm	0.9852	3436.48

Table 01: Representation of Enhancement constant (K_S) and Detection limit (LOD) for PK^1-2 obtained using Fluorescence titration spectra.

(2.2) Theoretical studies:

To gain detailed insight into the binding process and validate the experimental results, further computational work has been performed using Becke’s three-parameter hybrid exchange (B3LYP) in the Gaussian 16, Revision B.01b [37-40]. The 6-311G (d,p) and 6-31G (d,p) basis sets were utilized for all the elements. The geometric structures of the complex in the ground state (singlet) were fully optimized at the B3LYP levels. The effect of solvent (Acetonitrile: Water) was systematically monitored for all the steps via conductor-like Polarizable Continuum Model (PCM). Docking images have been visualized using Biovia discovery studio viewer [41,42].

The optimized structures (SI Figure S15-16) have been unitized for the docking study. The optimization of geometry for receptors in solvent and gas phases are presented in the Table 02. The binding energy of PK¹-SS (Figure 04) and PK²-SS (Figure 05) are -215.44 kcal/Joule and -220.85 kcal/Joule, respectively. The Binding behavior has been confirmed through docking study which suggests that strong binding between ligand and analyte is the result of π- π stacking and non-covalent π-sulfur interactions. Docking results reveal the change in bond length of ligand upon introduction of analyte, this suggests the disruption in bond energy of ligands.

Table 02: Geometry optimization table of receptor PK^1-2.

Sr. No	Name	Basis set	Phase	Optimization Energy Hatrees	Difference	E HOMO (eV)	E LUMO (eV)	Difference (eV)
Sr. No	Name	Basis set	Phase	Optimization Energy Hatrees	Difference	E HOMO (eV)	E LUMO (eV)	Difference (eV)
1	PK¹	6-31g(d,p)	Gas	-6879.928686	0.032501	-5.72	-1.326	-4.394
2	PK¹	6-31g(d,p)	Acetonitrile: water	-6879.961187	0.032501	-6.218	-1.635	-4.583
3	PK¹	6-311g(d,p)	Gas	-6880.924028	0.035942	-5.936	-1.592	-4.344
4	PK¹	6-311g(d,p)	Acetonitrile: water	-6880.95997	0.035942	-6.42	-1.886	-4.534
5	PK²	6-31g(d,p)	Gas	-7037.190773	0.033395	-5.72	-1.289	-4.431
6	PK²	6-31g(d,p)	Acetonitrile: water	-7037.224168	0.033395	-6.195	-1.586	-4.609
7	PK²	6-311g(d,p)	Gas	-7038.220885	0.037016	-5.939	-1.56	-4.379
8	PK²	6-311g(d,p)	Acetonitrile: water	-7038.257901	0.037016	-6.403	-1.843	-4.56

(2.3) Binding Constant:

A nonlinear regression approach was used to understand the Host (PK^1-2) – Guest (pesticide) interaction for more reliable association parameters [43]. An open-access program i.e.; supramolecular.org was used to obtain association constant and ratio using absorption titration data [44]. From the binding model, the fitting prefers 1:1 stoichiometry and association constant for PK^1-2 were calculated as 2.1 X 10⁴M^-1 and 2.23 X 10⁴ M^-1 respectively. The Association constant values are summarized in Table 03 and their direct links are available in Supporting Information (Table S1).

Association Model (1:1)	Experiments	Association Constant (K_a) (± Error%)	Mean K (± Error%)
PK¹	Exp-1	21024.39 (±1.29%)	21021.70 (± 1.18%)
	Exp-2	21086.56 (± 1.03%)
	Exp-3	20954.17 (± 1.24%)
PK²	Exp-1	22007.96 (± 0.72%)	22357.57 (± 0.93%)
	Exp-2	22528.69 (±0.99%)
	Exp-3	22536.07 (± 1.10%)

Table 03: Representation of Binding constant (K_a) value obtained using free online software (Supramolecular.org) accessed on November 2022.

(2.4) MALDI-TOF Studies:

To further confirm 1:1 binding of Sulfosulfuron and both the receptors, MALDI-TOF spectrometric technique was used [34]. In Acetonitrile: Water (9:1) mixed solvent system, Receptor (PK^1/2) and Pesticide (Sulfosulfuron) reaction results in 1:1 adduct formation showing m/z peak (Figure 06) at 1863.445 for [PK¹ + SS + H⁺] and 1919.483m/z for [PK² + SS + H⁺]. Sample preparations were briefly mentioned in Material and method section. (SI Page no. S6)

In the fluorescence spectra of receptor PK^1-2, along with excimer peak, two monomeric peaks were also observed due to intramolecular charge transfer within the molecule. After the incremental addition of Sulfosulfuron along with Enhancement in the spectra, both monomeric and excimer peak disappear resulting in one strong emission band [45]. The excimer and monomeric peaks in the spectra can be attributed to PET (Photoelectron transfer) arising from the sulfonyl to phenyl group which on addition of Sulfosulfuron stops and gives enhancement in the spectra as charge now migrate from sulfonyl to the indenyl ring present on Sulfosulfuron. (Figure 07 and SI Figure S19).

In the interference studies, along with Sulfosulfuron, five other relevant pesticides were considered (Ametryn, Chlorsulfuron, Metalaxyl, Pendimethalin, and Terbutryn). No notable change in the fluorescence spectra was observed (Figure 08) and the peak at 378 nm and intensity in fluorescence similar as [PK¹ + SS] was obtained. To confirm more selectivity, Chlorsulfuron (CS) which belongs to same herbicide family with Sulfosulfuron was taken, but no change in the fluorescence spectra with [PK¹ + CS] was observed (Supporting Information Figure S19).

The reversible nature of receptors with Sulfosulfuron were analyzed with acid-base treatment. In the following process, the quantitative fluorescence studies were carried out with Sulfosulfuron using both receptors PK^1-2 in MeCN: Water system (9:1 v/v) (Figure 09 and SI Figure 20). In the emission spectra, the band at 393 nm undergoes blue shift to 373 nm and the intensity in the fluorescence spectra rises upon the addition of Sulfosulfuron due to interaction with it. 0.5N HCl was added to the above solution resulting a decrease in the intensity of fluorescence spectra and the band shifts from 373 nm to 390 nm. To this, a freshly prepared 0.5N NaOH solution was added which results in the shift in the band again to its original position. This observation led us to the conclusion of reversible nature of the binding process of ligands towards Sulfosulfuron which can be employed without the use of any chelating agent using simple acid-base treatment [46]. The probable pictorial representation for rise and fall in the emission intensity due to acid-base treatment is displayed in the Figure 10.

In conclusion, we designed two fluorescent probes for selective detection of Sulfosulfuron among other relevant pesticides and herbicides by aqueous phase studies. The UV-Vis spectroscopy, Fluorescence spectroscopy and Mass spectrometric techniques conclude the selective detection of Sulfosulfuron in 1:1 stoichiometric complex formation, which was further confirmed through geometry optimization and docking study of receptors and Sulfosulfuron using the same solvent system. The Binding constant values for PK^1-2were 2.1 X 10⁴ M^-1 and 2.23 X 10⁴ M^-1respectively whereas the LOD values were determined to be 0.21 ppm and 0.35 ppm respectively. The Enhancement constant (Ks) value was found out to be7.07 X 10⁴ M^-1and 5.55 X 10⁴ M^-1 for PK¹ and PK² respectively. The receptors were found to be completely recyclable in nature using simple Acid-Base treatment. This new approach of sensing toxic pesticides at micro-level concentration develops interest for further modification in the field supramolecular sensors.

Acknowledgement:

Central University of Gujarat (CUG), Indrashil University (IU), CSIR-CSMCRI (Central Salt and Marine Chemicals Research Institute), PDEU (Pandit Dindayal Energy University), and IIT-Indore are acknowledged for providing instrumental facilities. The authors are thankful to INFLIBNET for e-journal access and Gujarat University (GU) for providing research infrastructure. Dr. V.K Jain is acknowledged for giving access to spectroscopic instruments.

Author Contributions:

Priyanka Kashyap: Investigation; Conceptualization; Data curation; Formal analysis; Writing-original draft; Review and editing;

Dushyantsingh Rajpurohit: Formal analysis; Methodology; Validation; Visualization; Review and editing; Krunal Modi: Software; Validation; Writing - review & editing;

Hinaly Bhasin: Formal analysis; Writing - review & editing;

Patrick Fernandes: Validation;Data curation; Review and editing;

Divya Mishra: Project administration; Resources, Validation, and Funding acquisition.

Funding: The presented work was supported by Department of Chemistry, Gujarat University.

Data availability/ Availability of data and Materials: The detail of Materials and Methodology such as: Synthesis, Characterization, Photophysical data which were employed during the research along with the Comparison table have been included as an Electronic Supporting Information.

Code Availability: Not applicable.

Ethics Approval: For this work, the ethical approval was not required and no animals were harmed during the research.

Consent to Participate: All authors gave their consent to participate in the research.

Consent for Publication: All authors gave their consent to participate in the publication of this work.

Conflict of Interest: The authors declare no competing of financial or personal interest that could have appeared to the work displayed in the paper.

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08 Jan, 2023
Editor assigned by journal
06 Jan, 2023
Submission checks completed at journal
05 Jan, 2023
First submitted to journal
03 Jan, 2023

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Benzene Sulfonyl Linked Tetrasubstituted Thiacalix[4]arene for Selective and Sensitive Fluorometric Sensing of Sulfosulfuron Along with Theoretical Studies

Status:

Journal Publication

Version 1

Abstract

Figures

(1) Introduction

(2) Result And Discussion

(3) Probable Binding Mechanism

(4) Interference Studies

(5) Recyclability Studies

(6) Conclusion

Declarations

References

Additional Declarations

Supplementary Files

Status:

Journal Publication

Version 1