Fluorescence Quenching and the Chamber of Nitroaromatics: A Dinaphthoylated Oxacalix[4]arene’s(DNOC) Adventure Captured through Computational and Experimental Study

doi:10.21203/rs.3.rs-3397275/v1

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Fluorescence Quenching and the Chamber of Nitroaromatics: A Dinaphthoylated Oxacalix[4]arene’s(DNOC) Adventure Captured through Computational and Experimental Study

https://doi.org/10.21203/rs.3.rs-3397275/v1

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published 23 Nov, 2023

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This research introduces Dinaphthoylated Oxacalix[4]arene (DNOC) as a novel fluorescent receptor for selective detection of nitroaromatic compounds (NACs). DNOC was characterized using ¹H-NMR, ¹³C-NMR, and ESI-MS spectroscopic techniques. The receptor exhibited remarkable selectivity in acetonitrile towards various nitroaromatic analytes, including MNA; 2,4-DNT; 2,3-DNT; 1,3-DNB; 2,6-DNT and 4-NT as confirmed through emission spectra analysis. Investigation of binding constants, Stern-volmer analysis, lowest of detection limit (3σ/Slope) and fluorescence quenching sheds light on DNOC's inclusion behaviour. Additionally, Density Functional Theory (DFT) calculations using Gaussian 09 program elucidate the selectivity trend of the ligand DNOC for NAC detection. Analysing energy gaps between molecular orbitals (HOMO and LUMO) offers insights into electron-transfer mechanisms and electronic interactions. Smaller energy gaps indicate higher selectivity through favourable electron-transfer processes, while larger gaps imply reduced selectivity due to weaker electronic interactions. This interdisciplinary study combines experimental and computational approaches to comprehensively understand DNOC's selective binding behaviour, rendering it a promising chemical sensor for nitroaromatic explosives.

Fluorescence

Oxacalix[4]arene

Nitroaromatics

Host-guest complex

Quenching efficiency

DFT investigation

In the scientific community, rational approaches for synthesizing desired structures to address specific properties are highly attractive, particularly when expanding research fields. In sensing, the detection of toxic hazardous water contaminants necessitates a sensor with key characteristics: high luminescence, cost-effectiveness, ultra-sensing, and ultra-detection ability, rapid response time, multicycle reusability, and construction from readily available low-cost materials for economic viability [1, 2]. As a result, significant efforts have been dedicated to the synthesis and development of reliable sensors for real-time applications. The need for a reliable sensor for nitroaromatic explosives arises from their widespread use in various industrial, military, and terrorist activities [3]. Nitroaromatic compounds are key components in the production of explosives, propellants, and fireworks. For national security and criminal investigations, as well as environmental and human health, the identification of life-threatening explosives is critical.[4–6] The detection of explosives, particularly the widely used nitroaromatics, has become an important issue that involves cost-effective, more sensitive, and smaller technologies due to counter-terrorism and nature conservation concerns.[7–9] Conventional methods for detecting these compounds often involve laborious and time-consuming processes, which hinder their real-time monitoring and immediate response in critical situations. Therefore, there is a pressing demand for a high-performance sensor that can quickly and selectively detect trace amounts of nitroaromatics in water sources, soil, and air, enabling timely intervention and mitigating potential threats to human health and the environment. Raman spectroscopy, gas chromatography, fluorescence spectroscopy, mass spectroscopy, and X-ray imaging have been some of the analytical method used to detect explosives.[10–16] Fluorescence sensing has lately gotten a lot of interest since it has a lot of desirable characteristics including low cost, broad range detection, and high sensitivity.[17–20] Nitro explosives are nitro-aromatic compounds (NACs) that lack electrons and might turn off the fluorescence of an electron-rich probe via photo-induced electron transfer (PET) and intramolecular charge transfer (ICT).[20] As a result, nearly all fluorescence probes coupled to electron-rich functional groups exhibit a sensitive fluorescence response to electron-deficient explosives.[17, 21] The vast majority of efforts devoted to detecting explosives have focused on individual explosives, which are incapable of detecting a wide variety of explosives.[20]

Calix[4]arenes are classified as a supramolecular class of the third generation. Calix[4]arenes are a well-known class of supramolecules capable of adhering to electro-rich substances. Oxacalixarenes (OC) are a well-known heteracalixarene derivatives that contain oxygen as the bridge atom.[22] These macrocycles are easily available since they can be produced in a single step at room temperature using high yield nucleophilic aromatic substitution reaction.[23] Additionally, OCs have been implemented as fluorescence sensors for a variety of anionic and non-ionic guest analytes.[24, 25] These unique characteristics enable them to interact selectively and efficiently with a wide range of analytes, making them ideal candidates for sensor applications. Naphthalene derivatives, on the other hand, exhibit strong fluorescence properties, offering an excellent platform for the detection of target analytes through fluorescence quenching or enhancement mechanisms.[26–29] The electron-rich nature of naphthalene-based derivatives makes them particularly attractive for the development of nitroaromatic explosive sensors. They facilitate host-guest complexation through a charge transfer mechanism between the electron-rich part of the ligand and the electron-withdrawing nature of the analyte, leading to enhanced sensitivity and selectivity.[30, 31] This phenomenon enables the sensor to effectively detect a broad range of nitroaromatic explosives with heightened accuracy. Combining these two distinct components in a synergistic manner results in a sensor with unparalleled sensitivity and selectivity for nitroaromatic explosives. The oxacalixarene-naphthalene sensor offers several other advantages, such as cost-effectiveness, ease of synthesis, and potential multicycle reusability, making it a promising candidate for real-time detection and monitoring of hazardous water contaminants.

This breakthrough sensor design opens up new avenues for the field of analytical chemistry and environmental science, and its application holds promise for addressing critical challenges in environmental monitoring and public safety. By providing a reliable and efficient solution for detecting a wide variety of explosives, this research contributes significantly to the expanding domain of sensor technologies, catering to diverse real-world applications

In this research, we synthesized a novel di-naphthoylated oxacalixa[4]arene (DNOC) for selective detection of N-Methy-4-Nitroaniline (MNA); 4-Nitro toluene (4-NT); 2,4-Dinitro toluene (2,4-DNT); 2,3-Dinitro toluene (2,3-DNT); 2,6-Dinitro toluene (2,6-DNT); and 1,3-Dinitrobenzene (1,3-DNB). The fluorescence technique displayed high sensitivity and multi-sense for MNA; 2,4-DNT; 2,3-DNT; 1,3-DNB; 2,6-DNT and 4-NT among various NACs. Additionally, DFT studies established selectivity trends, and fluorescence investigations, including titration, Stern-Volmer study, and B-H plots for binding constant, provided insights into the binding interactions, making DNOC a promising fluorescence sensor for a wide range of NACs with potential applications in environmental monitoring and public safety.

2.1 Chemicals and Reagents

All used in the synthesis like 1-napthoyl chloride and triethylamine were purchased from Sigma-Aldrich. All the explosive components were of the best grade commercially available. All the solvents employed for the synthesis were commercially available and used as received without further purification. The purity of the compounds and the progress of the reactions were monitored by TLC using pre-coated silica gel-aluminum plates (Type 60 F254, Merck, Darmstadt, Germany) and visualized via exposure to UV light.

2.2 Instrumentation

¹H NMR and ¹³C NMR spectra were obtained via a Bruker AV-(III)-400 MHz spectrometer using a BBFO probe. ESI mass spectra were obtained via a Micromass Quarter2 mass spectrometer (Utah, USA) with a capillary voltage of 3000 V and source temperature of 120 ^oC. Fluorescence spectra were obtained using a HORIBA FluoroMax-4 spectrofluorometer (Kyoto, Japan).

2.3 Synthesis of the receptor

The parent oxacalix[4]arene viz. 2,14-dihydroxy tetranitrooxacalix[4]arene(DHTNOC) was synthesized according to the reported literature procedure (Scheme S1) [23]. DHTNOC then reacted with naphthoyl chloride in presence of Dry acetone and Triethyl amine (TEA) at room temperature for 24 hr. The detailed synthesis procedures described below and characterization data are given in the supporting information (Figure S1-S3).

TEA (2.5 mmol) was added to a solution of (2,14-dihydroxy tetranitrooxacalix[4]arene) DHTNOC (0.5 mmol) in dry acetone (~ 25 mL), which was then stirred for 25 min at ambient temperature. The appropriate 1-naphthoyl chloride (~ 1.0 mmol) were added to this reaction mixture and stirred for 24 hr. at room temperature. The reaction was monitored by TLC. After completion of the reaction, the solvent was removed in vacuo. Next, 1 M HCl (40 mL) was added to the reaction mixture, and the precipitates were filtered, washed with water and dried in vacuo to obtain the desired compounds with yield of 69%. (Scheme 1).

2.4 Preparation of the stock solution

A stock solution of the receptor L (0.1 mM) was prepared in acetonitrile for fluorescence studies. All the stock solutions of NACs (4-NT; MNA; 2, 4-DNT; 2, 3-DNT; 1, 3-DNB; TNP; 4-NP and 2, 6-DNT) were prepared in acetonitrile (1 mM) for Spectrofluorometer measurements. The solution was excited at 289 nm and the emission measurements were carried out within a range of 300–700 nm keeping the excitation and emission slit width of 5 nm.

2.5 Computational methods

In this research, we have utilized Density Functional Theory (DFT) at the B3LYP/6-31G (d) level of the Gaussian 09 program to investigate the selectivity of the ligand DNOC for the detection of nitroaromatic explosives. Density Functional Theory (DFT) is a powerful computational tool used to predict and understand molecular interactions, making it valuable in studying the selectivity of chemical processes. By calculating the energy gaps between molecular orbitals, such as the HOMO and LUMO, DFT provides insights into the charge-transfer mechanisms and electronic interactions between molecules. To establish the trend of selectivity, researchers can compare these energy gaps for different molecular complexes or interactions. A smaller energy gap indicates a more favorable charge-transfer process, suggesting higher selectivity towards a specific molecule or functional group. On the other hand, a larger energy gap signifies weaker electronic interactions and thus reduced selectivity.[30, 31] By applying DFT studies to investigate the electronic properties and energy differences between multiple interactions we can establish the trend of selectivity.

3.1. Sensing of Nitroaromatic Compounds

It was observed that DNOC exhibited strong emissions at 381 nm when excited at 289 nm. The stability of the ligand was monitored by recording the emission spectrum of DNOC at an interval of 12 hours which shows a negligible variation in DNOC emission maxima up to 60 hours (Figure S4). Fluorescence study was performed to investigate the interaction of DNOC with various NACs in acetonitrile. Figure 1a shows the interaction of DNOC with various NACs. Significant quenching in emission maxima of DNOC by 99.24%, 95.45%, 96.26%, 82.65%, 73.13%, and 69.10% is observed in the presence of MNA; 2,4-DNT; 2,3-DNT; 1,3-DNB; 2,6-DNT and 4-NT respectively (Fig. 1b).

3.2. Sensitivity study

Emission spectra of DNOC with varying concentration of MNA; 2,4-DNT; 2,3-DNT; 1,3-DNB; 2,6-DNT and 4-NT in acetonitrile resulted in a considerable change in emission intensity. The fluorescence intensity of DNOC decreased gradually with the increasing concentration of MNA; 2,4-DNT; 2,3-DNT; 1,3-DNB; 2,6-DNT and 4-NT. (Fig. 2). The Stern-Volmer equation was utilized to comprehend the binding interaction between DNOC and analytes. Plot of I₀/I vs. concentration of various analytes with the linear regression coefficient (R² ≈ 0.99) was determined (Figure S5). From the stern-volmer plot we discovered the effective range of detection for DNOC and various analytes complexes which was found to be 17.5 µM to 5 µM, 19 µM to 6 µM, 10 µM to 2 µM, 17.5 µM to 2.5 µM, 20 µM to 5 µM and 20 µM to 5 µM for MNA; 2,4-DNT; 2,3-DNT; 1,3-DNB; 2,6-DNT and 4-NT respectively. The Lowest Detection Limit (LOD) for each complex was derived by applying the Eq. 3.3σ/Slope (where σ = Standard deviation of blank solution) with stern-volmer plot values[32]. LODs were found to be 3.69µM, 5.10µM, 1.80µM, 1.23µM, 3.90µM and 3.49µM for MNA; 2,4-DNT; 2,3-DNT; 1,3-DNB; 2,6-DNT and 4-NT respectively. In contrast, table 2 provides a comparison of the LOD of some recently developed calixarene-based fluorescent probes to some commonly used nitroaromatic explosives. Benesi-Hildebrand equation for emission titration spectra is further employed to determine the binding affinity of the all the complexes via binding constant K_b (Fig. 2 inset)[33]. B-H plot of 1-(I₀-I) versus 1 / [Concentration of analyte] suggested good binding association between ligand and analyte complexes. The values of binding constant K_b from BH plot were found to be 0.2808×10⁵ M^− 1, 0.5070×10⁴ M^− 1, 2.4715×10⁵ M⁻1, 2.69×10⁴ M^− 1, 2.1965×10⁴ M^− 1 and 0.3819×10⁴ M^− 1 for MNA; 2,4-DNT; 2,3-DNT; 1,3-DNB; 2,6-DNT and 4-NT respectively. The lowest detection limit of calixarene-based fluorescent probes (2017–2022) is investigated, and we mentioned very few of them in comparison to the many different nitroaromatic explosives (Table 1).

Table 1

Comparison of lowest of detection limit of calixarene based fluorescent probes with different nitroaromatic explosives (2017–2022)
SSr. no.	Calixarene based fluorescent probes	Sensing method	Solvent	Analytes detected	Range/LOD	Ref.
1	Thiacalix[4]arene dinaphthalene sulfonate (TCDNS)	Fluorescence Spectroscopy	5%Water:THF	2-3-DNT	0.5 µM to 0.01 mM	[34]
1	Thiacalix[4]arene dinaphthalene sulfonate (TCDNS)	Fluorescence Spectroscopy	5%Water:THF	4-NT	4.0 µM to 0.1 mM	[34]
2	Calix-OCP-PPE	Fluorescence Spectroscopy	CHCl₃	2,4-DNT	190 ppb	[35]
2	Calix-OCP-PPE	Fluorescence Spectroscopy	CHCl₃	TNT	10 ppb	[35]
3	Calix[4]arene-containing phenylene-alt-ethynylene-carbazolylene polymers (Calix-PPE-CBZs)	Fluorescence Spectroscopy	CHCl₃	2,4-DNT	9.6ppm	[36]
4	Calix[4]arene containing quantum dot	Fluorescence Spectroscopy	Methanol	TNT	< 0.1 µg/mL.	[37]
4	Calix[4]arene containing quantum dot	Fluorescence Spectroscopy	Methanol	DNT	< 0.2 µg/mL.	[37]
5	oxacalix[4]arene appended N-(3-bromopropyl) phthalimide moieties (FON3PPh)	Fluorescence Spectroscopy	Acetonitrile	4-NT	2.4 µM	[38]
6	oxacalix[4]arene appended N-(3-bromopropyl) phthalimide moieties (PON3PPh)	Fluorescence Spectroscopy	Acetonitrile	2,6-DNT	0.1 µM	[38]
7	Tetra-Methoxy Resorcinarene-N-(2-ethyl) Phthalimide (TMRN2Ph)	Fluorescence Spectroscopy	5%Water:THF	4-NT	50 µM to 1 mM	[39]
8	DAQTNOC(5,17-di(N-(9,10-dioxo-9,10-dihydroanthracen1-yl)acetamide) tetranitrooxacalix[4]arene)	Fluorescence	Acetonitrile	MNA	50 nM to 0.5 mM	[40]
8		Fluorescence	Acetonitrile	MNA	50 nM to 0.5 mM	[40]

3.3. DFT Optimization Study

Chemical reactivity parameters are widely used to explain the reaction pathway mechanism and reactivity of any system. Energy and distribution of the frontier molecular orbitals (FMO) of a molecule helps to demonstrate these parameters and the active site present in it. The occupied orbitals represent the ability to donate electron whereas the unoccupied orbitals represent its electron accepting abilities[41–43]. The gap arising between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) orbital which is better known as the energy gap, determines the molecular transport properties, the measure of electron conductivity, stability, etc. of a system. The higher energy gap suggests higher molecular stability and less reactivity, while lower energy gap makes a system less stable, thus increasing reactivity[44, 45]. The electrophilicity index can offer valuable information about a molecule's electron-accepting tendencies and its potential interactions with other molecules or analytes. In the context of sensing applications, understanding the electrophilicity index of a ligand or sensor can help researchers predict its behavior and selectivity towards specific analytes, including nitroaromatic explosives or other electron-rich species.

3.3.1 DFT insight into DNOC:

Initially, the receptor DNOC was optimized using beckys three parametrized correlation function (B3LYP). The geometry optimized structure of the receptor indicates that, DNOC exhibits in an inverted cone structure with two naphthoyl ring derivatized at the lower rim (Scheme 1). The results obtained from the DFT calculations provide valuable insights into the electronic properties of the ligand (Fig. 3). The moderate energy gap between the HOMO and LUMO signifies the ligand's potential to engage in charge-transfer processes, indicating its ability to readily donate or accept electrons during chemical interactions. The intermediate hardness and relatively low softness values suggest that the ligand exhibits a balanced reactivity towards electron transfer reactions, making it moderately responsive to changes in its electronic environment. Moreover, the negative chemical potential indicates that the ligand possesses the capability to act as an electron donor, further enhancing its potential as an active participant in electron-transfer phenomena. These electronic characteristics collectively hint at the ligand's versatility in interacting with other molecules and provide valuable groundwork for exploring its potential application.

3.3.2 DFT Properties of DNOC Complex with different nitroaromatics:

The trend of selectivity in this study can be established based on the energy gap values of the analytes. As Fig. 4 suggests, among the tested analytes, 2-Nitroanisole (MNA) has the smallest energy gap, indicating a strong ability to accept electrons from the ligand or sensor, leading to the highest fluorescence quenching percentage. The subsequent analytes, 2,4-Dinitrotoluene, and 2,6-Dinitrotoluene, show slightly larger energy gaps but still promote significant fluorescence quenching. As the energy gap increases further, 1,3-Dinitrobenzene displays reduced fluorescence quenching compared to the previous analytes. 2,3-Dinitrotoluene and 4-Nitrotoluene, with the largest energy gaps, exhibit the lowest fluorescence quenching percentages among the tested analytes. Overall, the trend of selectivity is inversely proportional to the energy gap values, where smaller energy gaps correspond to higher fluorescence quenching and stronger interactions between the ligand and analytes, establishing the ligand's preference for specific nitroaromatic analytes. The quenching efficiency is also influenced significantly by the structure of the analytes.

3.4. Binding Behaviour

The quenching mechanism of DNOC could be attributed due to the energy transfer or electron transfer. As reported previously, the absorption of nitroaromatics is usually below 380 nm, and here the ligand shows excitation maxima at 381 nm, which leads us to believe that electron transfer plays crucial role in quenching of emission spectra. The observed trend of selectivity from DFT study slightly deviates from the experimental quenching efficiency. To this deviating phenomenon, contributing factor may have been due to the slightly electron donating nature of methyl group and electron withdrawing nature of nitro group in nitro-toluene compounds[46].

Binding behavior of nitroaromatics with DNOC can be explained due to the electron transfer from electron rich naphthalene moiety to the electron withdrawing nitroaromatic compounds as observed in DFT study. Further, complexation can be due to the π-π stacking interactions between the ligand's naphthalene rings and the analytes' aromatic moieties and π-cation interaction.

In this study we have successfully developed Dinaphthoylated Oxacalix[4]arene (DNOC) as a selective fluorescent receptor for the detection of nitroaromatic compounds (NACs). The receptor demonstrated specific affinity towards a range of NACs, showcasing its potential as a promising chemical sensor. From the fluorescent spectrometer studies, it is discovered that DNOC can sense multiple NACs. This study includes Stern-volmer plot and B-H plot calculation to gain insight about DNOC’s binding with each analyte. The experimental quenching trends correlated well with the predicted trends from Density Functional Theory (DFT) calculations, validating the use of computational approaches in studying selectivity. However, some deviations between the DFT-predicted trends and the experimental observations were noted. These deviations could be attributed to the subtle variations in molecular structures and environmental conditions.

Ethical Approval

Not applicable

Competing Interest

The authors declare no conflict of interest.

Author’s Contributions

Vishv Desai: Writing- Original draft preparation, Data curation, DFT study.

Manthan Panchal: Validation, Investigation.

Jaymin Parikh: Computational study (writing).

Krunal Modi: Formal analysis, Software.

Manoj Vora: DFT study, Writing- Reviewing and Editing.

Falak Panjwani: Methodology, Visualization.

Vinod K Jain: Supervision, Project administration, Funding acquisition.

Funding

The authors thank the financial assistance provided by LSRBDRDO, New Delhi, through the project scheme REF. No (LSRB-01/15001/M/LSRB-373/BTB/2020).

Availability of data and materials

Data will be available upon request.

da Filho C, Duarte BM, A.C., and, Rocha-Santos TAP (2022) Environmental monitoring approaches for the detection of organic contaminants in marine environments: A critical review. Trends in Environmental Analytical Chemistry 33:e00154
Liaquat H, Imran M, Latif S, Hussain N, Bilal M (2022) Multifunctional nanomaterials and nanocomposites for sensing and monitoring of environmentally hazardous heavy metal contaminants. Environ Res 214:113795
Majeed S, Junaid HM, Waseem MT, Mahmood T, Farooq U, Shahzad SA (2022) Receptor free fluorescent and colorimetric sensors for solution and vapor phase detection of hazardous pollutant nitrobenzene; a new structural approach to design AIEE active and piezofluorochromic sensors. J Photochem Photobiol A Chem 431:114022
Woodfin RL (2006) Trace chemical sensing of explosives. John Wiley & Sons
Ma H, Li B, Zhang L, Han D, Zhu G (2015) Targeted synthesis of core–shell porous aromatic frameworks for selective detection of nitro aromatic explosives via fluorescence two-dimensional response. J Mater Chem A Mater 3(38):19346–19352
Thomas SW, Joly GD, Swager TM (2007) Chemical sensors based on amplifying fluorescent conjugated polymers. Chem Rev 107(4):1339–1386
Steinfeld JI, Wormhoudt J (1998) Explosives detection: a challenge for physical chemistry. Annu Rev Phys Chem 49(1):203–232
Afzal A, Iqbal N, Mujahid A, Schirhagl R (2013) Advanced vapor recognition materials for selective and fast responsive surface acoustic wave sensors: A review. Anal Chim Acta 787:36–49
Agbaria RA, Oldham PB, McCarroll M, McGown LB, Warner IM (2002) Molecular fluorescence, phosphorescence, and chemiluminescence spectrometry. Anal Chem 74(16):3952–3962
Griffin TM, Popkie N Jr, Eagan MA, McAtee RF, Vrazel D, McKinly J (2005) Instrument response measurements of ion mobility spectrometers in situ: Maintaining optimal system performance of fielded systems. Chem Biol Sens VI 5795:54–64
Czarnik AW (1998) A sense for landmines. Nature 394(6692):417–418
Gottfried JL, De Lucia FC, Munson CA, Miziolek AW (2009) Laser-induced breakdown spectroscopy for detection of explosives residues: a review of recent advances, challenges, and future prospects. Anal Bioanal Chem 395(2):283–300
Caygill JS, Davis F, Higson SPJ (2012) Current trends in explosive detection techniques. Talanta 88:14–29
Kuligowski J, Quintás G, De la Guardia M, Lendl B (2010) Analytical potential of mid-infrared detection in capillary electrophoresis and liquid chromatography: A review. Anal Chim Acta 679(1–2):31–42
Cooks RG, Ouyang Z, Takats Z, Wiseman JM (2006) Ambient mass spectrometry. Sci (1979) 311(5767):1566–1570
Pablos JL, Trigo-López M, Serna F, García FC, García JM (2014) Water-soluble polymers, solid polymer membranes, and coated fibres as smart sensory materials for the naked eye detection and quantification of TNT in aqueous media. Chem Commun 50(19):2484–2487
Salinas Y, Martínez-Máñez R, Marcos MD, Sancenón F, Costero AM, Parra M, Gil S (2012) Optical chemosensors and reagents to detect explosives. Chem Soc Rev 41(3):1261–1296
Kartha KK, Babu SS, Srinivasan S, Ajayaghosh A (2012) Attogram sensing of trinitrotoluene with a self-assembled molecular gelator. J Am Chem Soc 134(10):4834–4841
Gopalakrishnan D, Dichtel WR (2013) Direct detection of RDX vapor using a conjugated polymer network. J Am Chem Soc 135(22):8357–8362
Desai V, Panchal M, Dey S, Panjwani F, Jain VK (2021) Recent Advancements for the Recognization of Nitroaromatic Explosives Using Calixarene Based Fluorescent Probes. J Fluoresc, 1–13
Germain ME, Knapp MJ (2009) Optical explosives detection: from color changes to fluorescence turn-on. Chem Soc Rev 38(9):2543–2555
Mehta V, Panchal M, Modi K, Kongor A, Panchal U, Jain VK (2015) The chemistry of nascent oxacalix [n] hetarene (n ≥ 4): a review. Curr Org Chem 19(12):1077–1096
Katz JL, Feldman MB, Conry RR (2005) Synthesis of functionalized oxacalix [4] arenes. Org Lett 7(1):91–94
Vora M, Dey S, Kongor A, Panchal M, Verma A, Padhiyar N, Jain VK (2022) Design of bi-pyrene functionalized oxacalixarene probe for ratiometric detection of Fe3 + and PO43-ions. J Mol Liq, 118601
Dey S, Modi K, Panchal U, Panchal M, Jain VK (2021) Detection of small molecular toxins using azacalix [4] arene architecture and its theoretical investigations. J Mol Liq 337:116337
Sutariya PG, Soni H, Gandhi SA, Soni SS, Prasad J (2021) A dual-response naphthalene-armed calix [4] arene based fluorescence receptor for Zr (IV) and Fe (II) via Ligand to metal charge transfer. Sens Actuators B Chem 331:129417
Quiroga-Campano C, Gómez-Machuca H, Moris S, Pessoa-Mahana H, Jullian C, Saitz C (2021) Synthesis of calix [4] arenes bearing thiosemicarbazone moieties with naphthalene groups: Highly selective turn off/on fluorescent sensor for Cu (II) recognition. J Mol Struct 1225:129125
Bhatti AA, Oguz M, Memon S, Yilmaz M (2017) Dual fluorescence response of newly synthesized naphthalene appended calix [4] arene derivative towards Cu 2 + and I–. J Fluoresc 27:263–270
Mao X, Yang L, Zou Z, Luo L, Zhang X, Tian D, Deng H, Li H (2015) Dye responsive optical-electrochemical-wettability on a naphthalene-appended calix [4] arene clicking surface. Sens Actuators B Chem 212:371–376
Zhang X, Chen S, Jin S, Zhang Y, Chen X, Zhang Z, Shu Q (2017) Naphthalene based lab-on-a-molecule for fluorimetric and colorimetric sensing of F – and CN – and nitroaromatic explosives. Sens Actuators B Chem 242:994–998
Bal M, Köse A, Özpaça Ö, Köse M (2023) Pyrene, Anthracene, and Naphthalene-Based Azomethines for Fluorimetric Sensing of Nitroaromatic Compounds. J Fluoresc, 1–13
Jiang Z-J, Lv H-S, Zhu J, Zhao B-X (2012) New fluorescent chemosensor based on quinoline and coumarine for Cu2+. Synth Met 162(23):2112–2116
Kumar RS, Kumar SKA (2019) Highly selective fluorescent chemosensor for the relay detection of Al3 + and picric acid. Inorg Chem Commun 106:165–173
Modi K, Panchal U, Patel C, Bhatt K, Dey S, Mishra D, Jain VK (2018) Dual in vitro and in silico analysis of thiacalix [4] arene dinaphthalene sulfonate for the sensing of 4-nitrotoluene and 2, 3-dinitrotoluene. New J Chem 42(4):2682–2691
Prata JV, Costa AI, Teixeira CM (2020) A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated calix [4] arene polymer. J Fluoresc 30(1):41–50
Barata PD, Prata JV (2020) Fluorescent Calix [4] arene-Carbazole-Containing Polymers as Sensors for Nitroaromatic Explosives. Chemosensors 8(4):128
Peveler WJ, Roldan A, Hollingsworth N, Porter MJ, Parkin IP (2016) Multichannel detection and differentiation of explosives with a quantum dot array. ACS Nano 10(1):1139–1146
Panchal M, Kongor A, Athar M, Modi K, Patel C, Dey S, Vora M, Bhadresha K, Rawal R, Jha PC (2020) Structural motifs of oxacalix [4] arene for molecular recognition of nitroaromatic explosives: Experimental and computational investigations of host-guest complexes. J Mol Liq 306:112809
Panchal U, Modi K, Dey S, Prajapati U, Patel C, Jain VK (2017) A resorcinarene-based turn-off fluorescence sensor for 4-nitrotoluene: Insights from fluorescence and 1H NMR titration with computational approach. J Lumin 184:74–82
Mehta V, Athar M, Jha PC, Kongor A, Panchal M, Jain VK (2017) A turn-off fluorescence sensor for insensitive munition using anthraquinone-appended oxacalix [4] arene and its computational studies. New J Chem 41(12):5125–5132
Sarkar U, Khatua M, Chattaraj PK (2012) A tug-of-war between electronic excitation and confinement in a dynamical context. Phys Chem Chem Phys 14(5):1716–1727
Sarkar U (2002) Ground and excited states reactivity dynamics of hydrogen and helium atoms
Desai AL, Bhatt K, Modi KM, Patel NP, Panchal M, Kongor A, Patel CN, Liška A (2022) Calix [4] pyrrole based scrupulous probe for track on of tryptophan: Host-guest interaction, in silico modeling and molecular docking insights. Chem Phys 554:111426
Bandyopadhyay P, Karmakar A, Deb J, Sarkar U, Seikh MM (2020) Non-covalent interactions between epinephrine and nitroaromatic compounds: A DFT study. Spectrochim Acta A Mol Biomol Spectrosc 228:117827
Sarkar U (2005) Formaldehyde decomposition through profiles of global reactivity indices
Li Y, Liu K, Li W-J, Guo A, Zhao F-Y, Liu H, Ruan W-J (2015) Coordination polymer nanoarchitecture for nitroaromatic sensing by static quenching mechanism. J Phys Chem C 119(51):28544–28550

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No competing interests reported.

Scheme1.tif
Scheme 1 Synthesis of Di-naphthoylated oxacalix[4]arene (DNOC)
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05 Oct, 2023
First submitted to journal
29 Sep, 2023

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Fluorescence Quenching and the Chamber of Nitroaromatics: A Dinaphthoylated Oxacalix[4]arene’s(DNOC) Adventure Captured through Computational and Experimental Study

Status:

Journal Publication

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Abstract

Figures

1. Introduction

2. Experimental section

2.1 Chemicals and Reagents

2.2 Instrumentation

2.3 Synthesis of the receptor

2.4 Preparation of the stock solution

2.5 Computational methods

3. Result and Discussion

3.1. Sensing of Nitroaromatic Compounds

3.2. Sensitivity study

3.3. DFT Optimization Study

3.3.1 DFT insight into DNOC:

3.3.2 DFT Properties of DNOC Complex with different nitroaromatics:

3.4. Binding Behaviour

4. Conclusion

Declarations

References

Tables

Additional Declarations

Supplementary Files

Status:

Journal Publication

Version 1