Terbium-Based Dual-Ligand Metal Organic Framework by Diffusion Method for Selective and Sensitive Detection of Danofloxacin in Aqueous Medium

Terbium-Based Dual-Ligand Metal Organic Framework by Diffusion Method for Selective and Sensitive Detection of Danofloxacin in Aqueous Medium | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Terbium-Based Dual-Ligand Metal Organic Framework by Diffusion Method for Selective and Sensitive Detection of Danofloxacin in Aqueous Medium Gurdeep Singh, Deepika Garg, Sanjay Kumar, Rajpal Verma, Ashok Kumar Malik This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-2684011/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 18 Sep, 2023 Read the published version in Environmental Science and Pollution Research → Version 1 posted 6 You are reading this latest preprint version Abstract A water-dispersible Tb(III)-based Metal Organic Framework (TBP) has been produced by diffusion technique using benzene-1,3,5-tricarboxylic acid (BTC) and pyridine as ligands at low-cost and accessible starting materials. The thermal stability, crystalline nature, and rod-shaped morphology of the synthesized TBP have been confirmed by thermogravimetric (TGA), crystallographic (PXRD), and morphological (FE-SEM) studies. Various spectroscopic techniques have been carried out for detailed qualitative, quantitative, and photoluminescence (PL) analyses. For the quick and precise identification of Danofloxacin (DANO), TBP can be used as a sensor in an aqueous medium with significant enhancement compared to various fluoroquinolone antibiotics (levofloxacin (LEVO), ofloxacin (OFLO), norfloxacin (NOR), and ciprofloxacin (CIPRO)) with low detection limit of 0.45 ng/mL (1.25 nM).According to in-depth mechanistic studies of the density functional theory (DFT) calculations and mode of action, hydrogen bonding interactions and photo-induced electron transfer (PET) are the major factors for turn-on enhancement behaviour of TBP to DANO. The advantages of TBP include simple recovery and reuse for at least three cycles without noticeable loss of sensitivity. All of these characteristics profoundly show how beneficial the detection of DANO in aqueous environments is for the security and safety of the public. Metal organic framework (MOF) Morphology Fluoroquinolone Antibiotics (FQs) Fluorescence sensing Danofloxacin (DANO) Turn-on enhancement Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Highlights A Dual-LigandMOF (TBP) was synthesized for the selective fluorescent detection of DANO. The excellent water stability of TBP confirmed, it is suitable for the sensing of fluoroquinolone antibiotics (FQs) in aqueous media. TBP has the significant advantage of its ability to be reused for at least 3 cycles without noticeably losing sensitivity. The fluorescent detection of FQs was successfully demonstrated by DFT calculations and hydrogen bonding. 1. Introduction Fluoroquinolone antibiotics (FQs), also refer as quinolones, quinolone carboxylic acids, pyridine carboxylic acids, and 4-quinolones, are a large and rapidly growing class of synthetic antibacterial medicines (Giguère and Dowling 2013). Nalidixic acid by Lesher synthesis et al. in 1962 marked the beginning of an important antibacterial drug family of antibacterial agents (Lesher et al. 1962 ). Earliest members of the fluoroquinolone family of antibiotics, such as norfloxacin, levofloxacin, ciprofloxacin, and ofloxacin, were introduced on the global pharmaceutical market nearly three decades ago (Charushin et al. 2014). FQs are formed by modifying the core structure of quinolones by introducing a fluorine group at C-6 and a piperazine derivative (or piperazinyl ) group at C-7 (table S1)(Sukul and Spiteller 2007). These antibiotics are effective to treat a variety of bacterial infections, including skin, soft tissues, bones, and joints infections, as well as respiratory tract and urinary tract infections (Liu 2010 ). FQs are accidentally released into the environment causing harm to aquatic and terrestrial species. Antibiotics are found in various parts of the environment, that’s why various research groups expressed their major concern. Robinson et al. investigated the toxic effects of seven FQs on various prokaryotic and eukaryotic aquatic species, including ciprofloxacin, lomefloxacin, ofloxacin, and levofloxacin (Robinson, Belden, and Lydy 2005). FQs are toxicologically significant in animal test models at high doses, and there are some evidence that FQs can affect the growth and normal reproductive processes of fish, water fleas, macrophytes, amphibians, and green algae at low environmental doses when persistent exposure to active forms of these compounds (Janecko et al. 2016 ). Nowadays, FQs can be determined with a variety of analytical procedures, including electrochemical sensors (Goyal, Rana, and Chasta 2012; Huang et al. 2008 ), gas chromatography (GC) (Cerkvenik-Flajs 2006 ), electrocatalytic oxidation and voltammetry (Zhang, Wei, and Ding 2014), capillary electrophoresis (CE) (Cheng, Fu, and Chou 2007), high-performance liquid chromatography (HPLC) (Han et al. 2011 ), liquid chromatography ultraviolet detection (LC-UV) (Cooper et al. 2005 ; Turiel, Bordin, and Rodrı́guez 2003), surface-enhanced Raman spectroscopy (SERS) (He et al. 2010 ), enzyme-linked immunosorbent assay (ELISA) (Adrian et al. 2012 ; Xing et al. 2020 ), and liquid chromatography-tandem mass spectrometry (LC-MS/MS) (Li, Dai, et al. 2020 ). Despite the significant advantages of sensitivity and selectivity, these techniques are time-consuming, labour-intensive, and expensive to operate due to the need for specialized equipment, extensive pre-treatment, and high operating costs. As a result, these methods are difficult to devise for on-site monitoring of FQs(Serebrennikova et al. 2020 ). Fluorescence detection thus offers a substitute for high selectivity, sensitivity, and accuracy, as well as low cost, quick and easy operation for detection of antibiotics. Metal organic frameworks (MOFs) take attracted considerable attention and growth over recent years. A set of crystalline organic-inorganic hybrid materials build up from metal ions or metallic assembly acts as nodes interconnected by the organic ligands as a bridge are known as Metal organic frameworks (MOFs), which have shown a number of applications in various fields like sensing (Achmann et al. 2009 ), catalysis (Lee et al. 2009 ), drug-delivery (Horcajada et al. 2010 ), bio-imaging (Wang 2017 ), magnetism (Humphrey and Wood 2004), photocatalysis (Zhang and Lin 2014), adsorption and gas storage/separation (Al-Kutubi et al. 2015 ) due to their versatile properties such as well-defined crystal structure, high surface area, porosity, low density, high surface to volume ratio, high pore volume, and chemical tunability (Caskey and Matzger 2009; Lu et al. 2014 ). Fluorescent MOFs, proved one of the most promising sensing materials for detecting environmental contaminants, such as heavy metallic ions (Wang et al. 2017 ), explosives (Wang et al. 2016 ), and persistent organic pollutants (Wang et al. 2019 ), These materials revealed high sensitivity and a fast response time (Cui et al. 2012 ; Lustig et al. 2017 ; Wang, Lustig, and Li 2018 ). Antibiotic sensing with MOFs has received relatively little attention (Pan et al. 2018 ). The significant obstacles in the development of MOFs for FQs detection are improved sensitivity and aqueous stability. (Zhong et al. 2020 ). These challenges invoke us to develop the desired MOF sensors with stability in the aqueous medium. In the current work, pyridine and benzene-1,3,5-tricarboxylic acid (BTC) were chosen as ligands to construct water-stable MOFs having strong interactions of linkers with metal cations. These ligands were preferred because of their affordability and ease of synthesis. In this research paper, TBP, a fluorescent MOF has been synthesized by facile diffusion method using low-cost ligand precursors (BTC and pyridine). To the best of our knowledge, this study is the first detailed assessment towards the quantitation of DANO by using TBP. DANO has quickly and precisely been recognized by TBP in the aqueous medium with a detection limit (LOD) of 0.45 ng/mL (1.25 nM). Theoretical results have provided a full explanation for evidence of forward reaction steps and found a significant correlation between experimental and theoretical work. As a result, the current study is expected to shed more light on the chemical, structural, and spectroscopic features of synthesized compounds. 2. Experimental 2.1. Materials and Reagents Terbium nitrate pentahydrate (Tb(NO 3 ) 3 .5H 2 O), benzene-1,3,5 tricarboxylic acid (BTC), pyridine, and fluoroquinolone antibiotics (FQs): levofloxacin (LEVO), norfloxacin (NOR), ofloxacin (OFLO), danofloxacin (DANO), ciprofloxacin (CIPRO)were purchased from Sigma-Aldrich (Mumbai, India). Hydrochloric acid, and sodium hydroxide were purchased from Loba Chemie (Mumbai, India). All the compounds listed above were analytical-grade reagents. 2.2. Measurements On Perkin Elmer RXIFT-IR Spectrophotometer (Japan), the Fourier transform infrared (FT-IR) spectra of the ligands and TBP were scanned in the 400–4000 cm − 1 range. With the help of Panalytical’s X’Pert Pro Powder X-ray Diffractometer [CuKα X-ray ( λ = 1.54Å), 45 kV, and 40 mA], PXRD diffractograms for the determination of crystal structure were acquired. Morphological and topographical examinations of synthesized MOF were conducted using a Hitachi SU8010 Series (Japan) Field Emission Scanning electron microscope (FE-SEM). Energy-dispersive X-ray (EDX) spectrometer was used to obtain the EDX spectrum supplied as a surplus FE-SEM accessory (Hitachi SU8010 Series, Japan) mounted firmly on the stub of the specimen. The thermogravimetric analysis (TGA) was performed on Hitachi STA7300 (Japan) with a range of temperature from 35 o C to 800 o C (heating rate = 10 o C/min) in the atmosphere of pure nitrogen. For photoluminescence (PL) studies, a Shimadzu RF-5301PC spectrofluorometer (Japan) was used. 2.3. General Procedure for the synthesis of TBP: The Tb(III)-based MOF (TBP)was synthesized byadopting the diffusion technique (Scheme 1 ). Ligand solution (0.2 mmol of BTC and 1 mmol of pyridine) and metal solution (0.2 mmol of Tb(NO 3 ) 3 .5 H 2 O) were prepared separately in ethanol (10 mL), and deionizedwater (10 mL), respectively, and both solutions were sonicated for5 minutes. Firstly, metal solution (2 mL) was poured into a glass test tube and then ligand solution (2mL) was added to the same tube carefully along the sidewalls of the test tube.This resulted in the layer formation between metal and ligand solution. Then the glasstube was placed on a stand without disturbing the formed layer. For the better formation of the MOF crystals, the metal-ligand solution was kept undisturbed for five days. Whitecrystalline solid particles were obtained near the middle layer. The product (TBP) was collected after centrifugation (8000 rpm) and washing with ethanol (5 times) and water (5 times). The finally obtained MOF crystals were driedand shifted to a desiccator to keep them in a moisture-free state. 2.4. Luminescent Sensing A stock solution for photoluminescence analysis was prepared by dissolving 1 mg of excellently ground TBP in 100 mL of deionizedwater and sonicating it for 20 minutes. The photoluminescence sensing studies on the above-mentioned stock solution were carried out at room temperature. Because of its intriguing luminous behaviour, the potential uses of TBP as a photoluminescence sensing material for the identification of several FQs were investigated. The analyte solutions (LEVO, OFLO, NOR, CIPRO, and DANO) were prepared in water as a 3 ng/mL aqueous solution. Various concentrations of analyte solutions were made by dilution of a 3 ng/mL solution for a thorough investigation of selective detection of FQs. A good selective analysis was done by taking 100 µL of TBP stock solution mixed with 2.9 mL (3 ng/mL)of given FQs to make the total volume up to 3 mL. For all luminescent measurements, the photoluminescence spectra were recorded using a spectrofluorometer with λ ex = 353 nm and slit widths of 5 nm and 3 nm for excitation and emission monochromators, respectively. 3. Results and Discussion 3.1. Synthesis and Characterization of Terbium MOF (TBP) TBP was synthesized using the diffusion technique with an equimolar amount of terbium nitrate pentahydrate and BTC (with an excess of pyridine). Scheme 1 depicts the overall synthesis process. 3.1.1. FT-IR The presence of functional groups in TBP was confirmed using FT-IR determinations as shown in Fig. 1 . The characteristic bands have been observed for pyridine i.e., 1437, and 1581 cm − 1 corresponding to C = N and C = C respectively. BTC has shown broad stretch for O-H at 2843 cm − 1 , and other stretching bands at 1694, and 1267 cm − 1 resultant to the carbonyl of carboxylic acid and C-O in that order. Moreover, some new stretching bands have been found in TBP i.e. 1610 − 1553, 1434 − 1370, 511, and 457 cm − 1 belong to the stretching of the asymmetric and symmetric carboxylic groups, C = N, Tb-O, and Tb-N respectively. Absence of two major stretching bands in pyridine and BTC i.e. Tb-O, and Tb-N but present in TBP confirms the appropriate bonding of both ligands with Tb 3+ in TBP. Such types of stretching frequencies have confirmed the formation of TBP. 3.1.2. PXRD For crystallographic investigation of TBP under the current experimental system, PXRD was performed (Fig. 2 ). In comparison to the relative positions of the peaks, the diffraction peaks observed for synthesized TBP at the 2 θ scale matched closely with the standard diffraction pattern obtained for the Tb-MOF synthesized by stirring method (Bhardwaj et al. 2016 ). This result reveals that the TBP synthesis was successful. Moreover, the crystalline nature of TBP was also examined with the help of PXRD. The recorded PXRD diffractograms showed sharp peaks at 9.98, 10.26, 13.52, 17.45, 17.96, 20.56, and 31.09 having miller indices (100), (010), (001), (110), (101), (111), and (210) respectively which demonstrated the crystalline structure of the synthesized TBP. The average size (D) of the crystalline sample was estimated with the help of the Debye-Scherrer equation ( D = λK/ βcosθ , where K is the shape factor having value 0.89, λ denotes the X-ray wavelength having value 0.15406 nm, β is full width at half maxima (FWHM) and θ denotes the Bragg’s diffraction angle) and it was found to be 46.26 nm. 3.1.3. TGA The TGA was applied to examine the thermal stability of the synthesized TBP (Fig. 3 ). According to the first resulting curve, approximately 21.97% mass reduction occurred in the range of 50–115°C, which is related to processes of dehydration and de-solvation. It implies that in the previously mentioned range of temperature, the TBP loses the solvent moieties located in the pores. The next thermal curve after 465°Cresults from the collapse of the entire framework and the breakdown of the organic ligands. So, TBP was found to exist until 465°C, after that a fast weight reduction of approximately 42.03% occurred, indicating the breakdown of the TBP structure. 3.1.4. FE-SEM The topographical and structural morphology of the TBP was studied by FE-SEM. Figure 4 depicted FE-SEM micrographs of TBP at resolutions of x20,000, x40,000, x60,000, and x80,000. The synthesized TBP has shown a rod-shaped morphology, according to these micrographs. 3.1.5. EDX The existence of carbon (C), nitrogen (N), oxygen (O), and terbium (Tb) in TBP was revealed by compositional analysis of EDX spectra, with detected weights (atomic ratios) of 42.80% (63.28%), 2.17% (2.75%), 27.87% (30.93%), and 27.16% (3.03%), respectively (Figure S1). EDX investigation confirmed the high-purity MOF formation by demonstrating the existence of organic ligands and metal elements (O, C, N, and Tb) in the final structure of the TBP. 3.2. Detection of fluoroquinolones 3.2.1. Selectivity of TBP towards DANO Water was chosen as the solvent to examine the fluorescent sensing properties of TBP toward various FQs because TBP has good dispersion, high stability, and photoluminescent features in the aqueous medium. The spectra of PL emission of TBP dispersed in an aqueous medium were recorded at various excitations ranging from 323 nm to 383 nm (Figure S2). The maximum intensity of fluorescence emission was observed at λ ex = 353 nm. As a result, the excitation wavelength at 353 nm was chosen as the best excitation wavelength for further fluorescence studies to detect FQs. For selective analysis, the PL emission spectra of all suspensions (TBP/analyte) were observed and compared (Fig. 5 And Figure S3). The outcomes showed that each of the FQs under investigation enhanced the intensity of MOF. It is important to note that although other FQs exhibited a slight to moderate enhancement effect on fluorescence intensity, the contact between DANO and TBP significantly enhanced the luminescence. These results indicate that the TBP selectively detects DANO in an aqueous solution. 3.2.2. Sensitivity toward DANO TBP sensitivity to DANO was investigated by measuring the effect of DANO on PL emission intensity at λ ex = 353 nm (Fig. 6 ). Remarkably, PL emission increased with increasing DANO concentration. The Stern-Volmer (SV) equation reveals a linear relation between analyte molar concentration (C) and relative luminescent emission intensity (RI) (Qu et al. 2020 ). In this case, It can be properly described as RI-1 = K SV ×[C], where RI represents relative intensity expressed by I/I o for enhancement, and I o /I for quenching. I o and I represent the intensity values of photoluminescence emission for TBP before and after the addition of DANO, and Ksv denotes the Stern-Volmer constant (M − 1 ). Up to 3 ng/mL (8.40 nM), the SV plot of TBP towards DANO was observed to be linear (Fig. 7 ). The LOD of TBP for DANO in an aqueous medium was determined to be 0.45 ng/mL (1.25 nM) considering the standard deviations (SD) measured using thrice frequent photoluminescence emission study of blank solutions. 3.2.3. Recyclability Recyclability is a crucial concern for sensors. So, it also looked at the PL emission characteristics of recovered TBP. It was found that the enhancement in TBP emission intensity following the addition of DANO remained essentially unchanged up to the third recycling cycle, demonstrating its significant value in sensing. The PXRD pattern and FT-IR of TBP were not altered by DANO addition (Fig. 8 ). These results revealed that interactions between DANO and TBP could produce the enhancement phenomenon, but these interactions were not powerful enough to destabilize the crystalline structure of TBP. 3.2.4. The Effect of pH and response time Using hydrochloric acid (0.1 M), and sodium hydroxide (0.1 M)solutions, the PL intensity of the system was calculated in the pH range of 5 to 9, and it was found that the operation is pH-dependent (Fig. 9 (A)). In solutions of acidic and basic media, it was discovered that the fluorescence intensity of DANO was lower. The highest fluorescence emission intensity was seen when DANO was added at 7 pH. So, pH 7 was chosen as the optimum pH for further investigation. The emission spectra of TBP-DANO suspension were monitored at intervals of 1 minute up to 10 minutes following excitation at 353 nm to carry out the time-dependent detection of DANO. Figure 9 (B) shows that after 1 minute, the fluorescence emission attained a constant value. The fluorescence emission intensity of the suspension remained nearly unchanged throughout the contact time between DANO and TBP, indicating that the DANO-induced fluorescence enhancement happened relatively fast. 3.2.5. Mechanism The interactions between MOF and analytes were studied to obtain a better knowledge of the detailed mechanism of turn-on fluorescence enhancement behaviour of TBP after the addition of FQs. Possible mechanisms of turn-on enhancement between TBP and DANO are (1) hydrogen bonding interactions and (2) Photo-induced electron transfer (PET). The presence of pyridine results in a large surface area of TBP and the probe contains a lot of hydroxyl and carboxyl groups, which allows it to make hydrogen bonds with DANO. Unique and effectual hydrogen-bond may be formed between the (1′s,4′s)-5′-Methyl-2′,5′ diazabicyclo[2.2.1]hept-2′-yl ring, hydroxyl, carboxyl, or fluorine of DANO and the carboxyl or hydroxyl groups of TBP (Figure S4). The fluorescence intensity of TBP with DANO was significantly increased under the same excitation. The synergistic effect of hydrogen bonding can aid in the development of larger fluorophores and chromophores (Hua et al. 2018). Further, it can explain the enhancement phenomenon for other FQs (LEVO, OFLO, NOR, and CIPRO) with the same mechanism as the similar hydrogen interactions are present in the case of each analyte, due to which it is difficult to justify different significant enhancement behaviour of DANO. Therefore, the outcomes recommend that only hydrogen bond interactions cannot completely justify the observed enhancement behaviour. Moreover, The PET mechanism may be recognized for the process of enhancement. An effective electron transfer between the MOF and analyte is required for PET to function. As it has been proposed for many other MOFs, the PET could govern extremely selective identification of FQs by the TBP. The turn-on enhancement resulted from the transfer of electrons from the E LUMO of analytes to the conduction band of TBP when photoexcited because the E LUMO of FQs (analytes) were higher than the E LUMO of TBP (Figure S5) (Li, Long, et al. 2020). The E HOMO and E LUMO energies of FQs and BTC were calculated using the Gaussian 09 package programme (Density-functional theory (DFT) study) by taking the basis set B3LYP/6-311G to verify the mechanism related to this turn-on enhancement (Fig. 10 ). The Frontier Molecular Orbital (FMO) theory established the existence of an easy transfer of electrons between E HOMO and E LUMO of reacting species. As shown in Fig. 10 , the difference between E LUMO of BTC and E LUMO of DANO was found to be less than that of other FQs, allowing electrons to easily transfer from E LUMO of DANO to E LUMO of TBP. This agrees well with the noted highest enhancement for TBP with DANO. This implies that the electron transfer process and H-bonding interactions interact to produce the observed enhancement response. 4. Conclusions The Tb (III)-based MOF (TBP) has been synthesized using a facile diffusion technique at room temperature under normal conditions for the selective detection of DANO. Structural stability of the synthesized TBP was demonstrated by its ability to be recycled.As TBP has fluorescence properties and remarkable water stability, an excellent approach for fluorescence detection of DANO in water has been developed by utilizing its features. Results indicate that TBP detects DANO specifically in an aqueous medium by producing a significant turn-on enhancement response with the LOD as low as 0.45 ng/mL (1.25 nM).The existence of hydrogen bonding and Photo-induced electron transfer between the TBP and DANO can be linked to the highest turn-on enhancement. The demonstration of the sensor for FQs detection in actual environmental and biological samples may fall under the purview of the expanded scope of this work. Declarations Acknowledgments One of the authors, Gurdeep Singh, is grateful to University Grants Commission (UGC), New Delhi, India, for providing a junior research fellowship. We are highly thankful to RSIC, Panjab University, Chandigarh, and the Department of Chemistry, Punjabi University, Patiala for spectroscopic analysis. Ethics approval There is no ethical approval required. Consent to participate All authors give consent to participate in the revision of the manuscript. Consent to publish All authors give consent to publish the paper. Author Contributions Gurdeep Singh and Deepika Garg has performed the experiment and written the paper. Sanjay Kumar, Rajpal Vermaand has written and edited the paper. All authors reviewed the manuscript.Ashok Kumar Malik has supervised the whole work. 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J Am Chem Soc 138:6204–6216 Wang B, Wang P, Xie L-H, Lin R-B, Lv J, Li J-R, Chen B (2019) A stable zirconium based metal-organic framework for specific recognition of representative polychlorinated dibenzo-p-dioxin molecules. Nat Commun 10:1–8 Wang B, Yang Q, Guo C, Sun Y, Xie L-H, Jian-Rong Li (2017) Stable Zr (IV)-based metal–organic frameworks with predesigned functionalized ligands for highly selective detection of Fe (III) ions in water. ACS Appl Mater Interfaces 9:10286–10295 Wang H, Lustig WP, Li J (2018) Sensing and capture of toxic and hazardous gases and vapors by metal–organic frameworks. Chem Soc Rev 47:4729–4756 Wang H-S (2017) Metal–organic frameworks for biosensing and bioimaging applications. Coord Chem Rev 349:139–155 Xing K-Y, Peng J, Shan S, Liu D-F, Huang Y-N, Wei-Hua L (2020) Green enzyme-linked immunosorbent assay based on the single-stranded binding protein-assisted aptamer for the detection of mycotoxin. Anal Chem 92:8422–8426 Zhang T, and Wenbin Lin (2014) Metal–organic frameworks for artificial photosynthesis and photocatalysis. Chem Soc Rev 43:5982–5993 Zhang, Xin Y, Wei, Ding Y (2014) Electrocatalytic oxidation and voltammetric determination of ciprofloxacin employing poly (alizarin red)/graphene composite film in the presence of ascorbic acid, uric acid and dopamine. Anal Chim Acta 835:29–36 Zhong W-B, Li R-X, Lv J, He T, Xu M-M, Wang B, Xie L-H, Li J-R (2020) Two isomeric In (III)-MOFs: unexpected stability difference and selective fluorescence detection of fluoroquinolone antibiotics in water. Inorg Chem Front 7:1161–1171 Scheme Scheme 1 is available in the Supplementary Files section Supplementary Files floatimage1.png Graphical Abstract floatimage2.png Scheme 1.Schematic representation for the formation of MOF (TBP) by diffusion method. Supplementaryinformation.docx Cite Share Download PDF Status: Published Journal Publication published 18 Sep, 2023 Read the published version in Environmental Science and Pollution Research → Version 1 posted Editorial decision: Major Revision 19 Jun, 2023 Reviewers agreed at journal 30 Apr, 2023 Reviewers invited by journal 24 Apr, 2023 Editor invited by journal 24 Apr, 2023 Editor assigned by journal 13 Apr, 2023 First submitted to journal 03 Apr, 2023 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-2684011","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":194686428,"identity":"f13d8a61-4341-455b-912d-61ca67a86a83","order_by":0,"name":"Gurdeep Singh","email":"","orcid":"","institution":"Punjabi University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Gurdeep","middleName":"","lastName":"Singh","suffix":""},{"id":194686429,"identity":"33df9d87-8113-4ed6-8e97-1006481629ff","order_by":1,"name":"Deepika Garg","email":"","orcid":"","institution":"Punjabi University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Deepika","middleName":"","lastName":"Garg","suffix":""},{"id":194686430,"identity":"a30c100c-f738-4789-9c59-ca8233cc1755","order_by":2,"name":"Sanjay Kumar","email":"","orcid":"","institution":"Multanimal Modi College Modinagar","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Sanjay","middleName":"","lastName":"Kumar","suffix":""},{"id":194686431,"identity":"4c0e0d85-18c6-4958-9705-b3e3ef7245e4","order_by":3,"name":"Rajpal Verma","email":"","orcid":"","institution":"Dr BR Ambedkar National Institute of Technology Department of Chemistry","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Rajpal","middleName":"","lastName":"Verma","suffix":""},{"id":194686432,"identity":"77d86309-fec5-43c2-886c-44da40767f6e","order_by":4,"name":"Ashok Kumar Malik","email":"data:image/png;base64,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","orcid":"","institution":"Punjabi University","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Ashok","middleName":"Kumar","lastName":"Malik","suffix":""}],"badges":[],"createdAt":"2023-03-12 15:22:36","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-2684011/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-2684011/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11356-023-29895-7","type":"published","date":"2023-09-18T15:01:18+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":36379049,"identity":"e0b45edd-1596-4d22-ad46-0cc1bb15ac9f","added_by":"auto","created_at":"2023-04-27 13:46:29","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":108615,"visible":true,"origin":"","legend":"\u003cp\u003eFourier transform infrared (FT-IR) spectra of TBP, BTC, and Pyridine.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/fc11e4957df253d1dfa2d1d1.png"},{"id":36379061,"identity":"88fa3db1-0a82-4f52-87c2-6caf2b72ce62","added_by":"auto","created_at":"2023-04-27 13:46:29","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":78370,"visible":true,"origin":"","legend":"\u003cp\u003ePowder X-ray diffraction (PXRD) Pattern of TBP.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/ee76d345448fc796582feb28.png"},{"id":36379755,"identity":"b5a14f82-157a-4122-893b-de8b8e92a5e3","added_by":"auto","created_at":"2023-04-27 14:02:29","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":80040,"visible":true,"origin":"","legend":"\u003cp\u003eThermogravimetric analysis (TGA) curve of TBP.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/eac167daec117d7d3093dcc9.png"},{"id":36379759,"identity":"eaf249fd-687d-4814-94b8-d27bf93c0067","added_by":"auto","created_at":"2023-04-27 14:02:29","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":611583,"visible":true,"origin":"","legend":"\u003cp\u003eFE-SEM micrographs of the TBP at various resolutions \u003cstrong\u003e(a)\u003c/strong\u003e x20,000; \u003cstrong\u003e(b)\u003c/strong\u003e x40,000; \u003cstrong\u003e(c)\u003c/strong\u003e x60,000; and \u003cstrong\u003e(d) \u003c/strong\u003ex80,000.\u003c/p\u003e","description":"","filename":"F4.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/b613a5853410a41e11af1f0b.png"},{"id":36379194,"identity":"d6585114-b153-4d57-9806-37df1c82a928","added_by":"auto","created_at":"2023-04-27 13:54:29","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":140664,"visible":true,"origin":"","legend":"\u003cp\u003eFluorescence spectra for TBP dispersed in the aqueous solution containing different FQs when excited at 353 nm.\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/4652c34f876313385beee884.png"},{"id":36379058,"identity":"ab874e52-946a-4b6f-9657-3d898b13d397","added_by":"auto","created_at":"2023-04-27 13:46:29","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":265117,"visible":true,"origin":"","legend":"\u003cp\u003eEnhancement in fluorescence emission of TBP upon continuous addition of a solution of DANO in the aqueous medium.\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/d9d5e370ed5e3b346439aa56.png"},{"id":36379050,"identity":"a47b4f28-3ec6-4897-8b53-982a0ec87a3c","added_by":"auto","created_at":"2023-04-27 13:46:29","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":57867,"visible":true,"origin":"","legend":"\u003cp\u003eThe stern-Volmer plot of TBP upon adding different concentrations of DANO.\u003c/p\u003e","description":"","filename":"floatimage9.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/0a29e99a19a39a3b84f0b801.png"},{"id":36379756,"identity":"6c5807d8-ab6f-4fb2-9726-a9c1da397924","added_by":"auto","created_at":"2023-04-27 14:02:29","extension":"jpeg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":292582,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(A) \u003c/strong\u003eThe Powder XRD patterns and \u003cstrong\u003e(B) \u003c/strong\u003eFT-IR of \u003cstrong\u003e(a) \u003c/strong\u003efresh TBP and \u003cstrong\u003e(b) \u003c/strong\u003eafter 3rd sensing cycle of DANO in the water.\u003c/p\u003e","description":"","filename":"floatimage10.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/80e00741175bcc63a36472bc.jpeg"},{"id":36379935,"identity":"2b0d9f42-af65-43cd-98cf-11cd2e9ccee2","added_by":"auto","created_at":"2023-04-27 14:10:29","extension":"jpeg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":180609,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of pH \u003cstrong\u003e(A)\u003c/strong\u003e and response time \u003cstrong\u003e(B)\u003c/strong\u003e on the fluorescent intensity of TBP upon the addition of the aqueous solution of DANO.\u003c/p\u003e","description":"","filename":"floatimage11.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/59e9b4d89e542722e15497a0.jpeg"},{"id":36379758,"identity":"997c4a1c-74db-4d1f-9517-f3f6b1f290c4","added_by":"auto","created_at":"2023-04-27 14:02:29","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":253060,"visible":true,"origin":"","legend":"\u003cp\u003eEnergy values and HOMO and LUMO plots of various FQs and organic ligand (BTC).\u003c/p\u003e","description":"","filename":"floatimage12.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/c13b6b9c34b8a3407b8e35cb.png"},{"id":43640505,"identity":"30cbc8f2-c866-4fd2-bbff-b739fda2e8e4","added_by":"auto","created_at":"2023-09-25 15:07:18","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1941923,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/044946c3-27a5-4b7a-a6ce-3dded2fe2cca.pdf"},{"id":36379190,"identity":"93d39269-83cb-4e1a-8aca-5202ab6bed07","added_by":"auto","created_at":"2023-04-27 13:54:29","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":448685,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGraphical Abstract\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/cf63f483a5fcb2e131e2cc56.png"},{"id":36379187,"identity":"7d7076f1-36ca-4935-b003-7e5c75bb1c03","added_by":"auto","created_at":"2023-04-27 13:54:29","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":262320,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1.\u003c/strong\u003eSchematic representation for the formation of MOF (TBP) by diffusion method.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/f3e0e468d46edb938badb4e0.png"},{"id":36379055,"identity":"7e1b0cc6-25ab-425d-8217-742c35513738","added_by":"auto","created_at":"2023-04-27 13:46:29","extension":"docx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":875800,"visible":true,"origin":"","legend":"","description":"","filename":"Supplementaryinformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-2684011/v1/c550663b75965349d6301136.docx"}],"financialInterests":"","formattedTitle":"Terbium-Based Dual-Ligand Metal Organic Framework by Diffusion Method for Selective and Sensitive Detection of Danofloxacin in Aqueous Medium","fulltext":[{"header":"Highlights","content":"\u003cul\u003e\n \u003cli\u003eA Dual-LigandMOF (TBP) was synthesized\u0026nbsp;for the selective fluorescent detection of DANO.\u003c/li\u003e\n \u003cli\u003eThe excellent water stability of TBP\u0026nbsp;confirmed, it is\u0026nbsp;suitable for the sensing of fluoroquinolone antibiotics (FQs)\u0026nbsp;in aqueous media.\u003c/li\u003e\n \u003cli\u003eTBP has the significant advantage of its ability to be reused for at least 3 cycles without noticeably losing sensitivity.\u003c/li\u003e\n \u003cli\u003eThe fluorescent detection of FQs was successfully demonstrated by DFT calculations and hydrogen bonding.\u003c/li\u003e\n\u003c/ul\u003e"},{"header":"1. Introduction","content":"\u003cp\u003eFluoroquinolone antibiotics (FQs), also refer as quinolones, quinolone carboxylic acids, pyridine carboxylic acids, and 4-quinolones, are a large and rapidly growing class of synthetic antibacterial medicines (Gigu\u0026egrave;re and Dowling 2013). Nalidixic acid by Lesher synthesis et al. in 1962 marked the beginning of an important antibacterial drug family of antibacterial agents (Lesher et al. \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e1962\u003c/span\u003e). Earliest members of the fluoroquinolone family of antibiotics, such as norfloxacin, levofloxacin, ciprofloxacin, and ofloxacin, were introduced on the global pharmaceutical market nearly three decades ago (Charushin et al. 2014). FQs are formed by modifying the core structure of quinolones by introducing a fluorine group at C-6 and a piperazine derivative (or piperazinyl ) group at C-7 (table S1)(Sukul and Spiteller 2007). These antibiotics are effective to treat a variety of bacterial infections, including skin, soft tissues, bones, and joints infections, as well as respiratory tract and urinary tract infections (Liu \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). FQs are accidentally released into the environment causing harm to aquatic and terrestrial species. Antibiotics are found in various parts of the environment, that\u0026rsquo;s why various research groups expressed their major concern. Robinson et al. investigated the toxic effects of seven FQs on various prokaryotic and eukaryotic aquatic species, including ciprofloxacin, lomefloxacin, ofloxacin, and levofloxacin (Robinson, Belden, and Lydy 2005). FQs are toxicologically significant in animal test models at high doses, and there are some evidence that FQs can affect the growth and normal reproductive processes of fish, water fleas, macrophytes, amphibians, and green algae at low environmental doses when persistent exposure to active forms of these compounds (Janecko et al. \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2016\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eNowadays, FQs can be determined with a variety of analytical procedures, including electrochemical sensors (Goyal, Rana, and Chasta 2012; Huang et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2008\u003c/span\u003e), gas chromatography (GC) (Cerkvenik-Flajs \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2006\u003c/span\u003e), electrocatalytic oxidation and voltammetry (Zhang, Wei, and Ding 2014), capillary electrophoresis (CE) (Cheng, Fu, and Chou 2007), high-performance liquid chromatography (HPLC) (Han et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2011\u003c/span\u003e), liquid chromatography ultraviolet detection (LC-UV) (Cooper et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2005\u003c/span\u003e; Turiel, Bordin, and Rodrı́guez 2003), surface-enhanced Raman spectroscopy (SERS) (He et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2010\u003c/span\u003e), enzyme-linked immunosorbent assay (ELISA) (Adrian et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Xing et al. \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2020\u003c/span\u003e), and liquid chromatography-tandem mass spectrometry (LC-MS/MS) (Li, Dai, et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Despite the significant advantages of sensitivity and selectivity, these techniques are time-consuming, labour-intensive, and expensive to operate due to the need for specialized equipment, extensive pre-treatment, and high operating costs. As a result, these methods are difficult to devise for on-site monitoring of FQs(Serebrennikova et al. \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Fluorescence detection thus offers a substitute for high selectivity, sensitivity, and accuracy, as well as low cost, quick and easy operation for detection of antibiotics.\u003c/p\u003e \u003cp\u003eMetal organic frameworks (MOFs) take attracted considerable attention and growth over recent years. A set of crystalline organic-inorganic hybrid materials build up from metal ions or metallic assembly acts as nodes interconnected by the organic ligands as a bridge are known as Metal organic frameworks (MOFs), which have shown a number of applications in various fields like sensing (Achmann et al. \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2009\u003c/span\u003e), catalysis (Lee et al. \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2009\u003c/span\u003e), drug-delivery (Horcajada et al. \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2010\u003c/span\u003e), bio-imaging (Wang \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2017\u003c/span\u003e), magnetism (Humphrey and Wood 2004), photocatalysis (Zhang and Lin 2014), adsorption and gas storage/separation (Al-Kutubi et al. \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2015\u003c/span\u003e) due to their versatile properties such as well-defined crystal structure, high surface area, porosity, low density, high surface to volume ratio, high pore volume, and chemical tunability (Caskey and Matzger 2009; Lu et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2014\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eFluorescent MOFs, proved one of the most promising sensing materials for detecting environmental contaminants, such as heavy metallic ions (Wang et al. \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2017\u003c/span\u003e), explosives (Wang et al. \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2016\u003c/span\u003e), and persistent organic pollutants (Wang et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2019\u003c/span\u003e), These materials revealed high sensitivity and a fast response time (Cui et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Lustig et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Wang, Lustig, and Li \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Antibiotic sensing with MOFs has received relatively little attention (Pan et al. \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). The significant obstacles in the development of MOFs for FQs detection are improved sensitivity and aqueous stability. (Zhong et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). These challenges invoke us to develop the desired MOF sensors with stability in the aqueous medium. In the current work, pyridine and benzene-1,3,5-tricarboxylic acid (BTC) were chosen as ligands to construct water-stable MOFs having strong interactions of linkers with metal cations. These ligands were preferred because of their affordability and ease of synthesis.\u003c/p\u003e \u003cp\u003eIn this research paper, TBP, a fluorescent MOF has been synthesized by facile diffusion method using low-cost ligand precursors (BTC and pyridine). To the best of our knowledge, this study is the first detailed assessment towards the quantitation of DANO by using TBP. DANO has quickly and precisely been recognized by TBP in the aqueous medium with a detection limit (LOD) of 0.45 ng/mL (1.25 nM). Theoretical results have provided a full explanation for evidence of forward reaction steps and found a significant correlation between experimental and theoretical work. As a result, the current study is expected to shed more light on the chemical, structural, and spectroscopic features of synthesized compounds.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials and Reagents\u003c/h2\u003e \u003cp\u003eTerbium nitrate pentahydrate (Tb(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e.5H\u003csub\u003e2\u003c/sub\u003eO), benzene-1,3,5 tricarboxylic acid (BTC), pyridine, and fluoroquinolone antibiotics (FQs): levofloxacin (LEVO), norfloxacin (NOR), ofloxacin (OFLO), danofloxacin (DANO), ciprofloxacin (CIPRO)were purchased from Sigma-Aldrich (Mumbai, India). Hydrochloric acid, and sodium hydroxide were purchased from Loba Chemie (Mumbai, India). All the compounds listed above were analytical-grade reagents.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Measurements\u003c/h2\u003e \u003cp\u003eOn Perkin Elmer RXIFT-IR Spectrophotometer (Japan), the Fourier transform infrared (FT-IR) spectra of the ligands and TBP were scanned in the 400\u0026ndash;4000 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e range. With the help of Panalytical\u0026rsquo;s X\u0026rsquo;Pert Pro Powder X-ray Diffractometer [CuKα X-ray (\u003cb\u003eλ\u003c/b\u003e\u0026thinsp;=\u0026thinsp;1.54\u0026Aring;), 45 kV, and 40 mA], PXRD diffractograms for the determination of crystal structure were acquired. Morphological and topographical examinations of synthesized MOF were conducted using a Hitachi SU8010 Series (Japan) Field Emission Scanning electron microscope (FE-SEM). Energy-dispersive X-ray (EDX) spectrometer was used to obtain the EDX spectrum supplied as a surplus FE-SEM accessory (Hitachi SU8010 Series, Japan) mounted firmly on the stub of the specimen. The thermogravimetric analysis (TGA) was performed on Hitachi STA7300 (Japan) with a range of temperature from 35\u003csup\u003eo\u003c/sup\u003eC to 800\u003csup\u003eo\u003c/sup\u003eC (heating rate\u0026thinsp;=\u0026thinsp;10\u003csup\u003eo\u003c/sup\u003eC/min) in the atmosphere of pure nitrogen. For photoluminescence (PL) studies, a Shimadzu RF-5301PC spectrofluorometer (Japan) was used.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. General Procedure for the synthesis of TBP:\u003c/h2\u003e \u003cp\u003eThe Tb(III)-based MOF (TBP)was synthesized byadopting the diffusion technique (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Ligand solution (0.2 mmol of BTC and 1 mmol of pyridine) and metal solution (0.2 mmol of Tb(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e.5 H\u003csub\u003e2\u003c/sub\u003eO) were prepared separately in ethanol (10 mL), and deionizedwater (10 mL), respectively, and both solutions were sonicated for5 minutes. Firstly, metal solution (2 mL) was poured into a glass test tube and then ligand solution (2mL) was added to the same tube carefully along the sidewalls of the test tube.This resulted in the layer formation between metal and ligand solution. Then the glasstube was placed on a stand without disturbing the formed layer. For the better formation of the MOF crystals, the metal-ligand solution was kept undisturbed for five days. Whitecrystalline solid particles were obtained near the middle layer. The product (TBP) was collected after centrifugation (8000 rpm) and washing with ethanol (5 times) and water (5 times). The finally obtained MOF crystals were driedand shifted to a desiccator to keep them in a moisture-free state.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Luminescent Sensing\u003c/h2\u003e \u003cp\u003eA stock solution for photoluminescence analysis was prepared by dissolving 1 mg of excellently ground TBP in 100 mL of deionizedwater and sonicating it for 20 minutes. The photoluminescence sensing studies on the above-mentioned stock solution were carried out at room temperature. Because of its intriguing luminous behaviour, the potential uses of TBP as a photoluminescence sensing material for the identification of several FQs were investigated. The analyte solutions (LEVO, OFLO, NOR, CIPRO, and DANO) were prepared in water as a 3 ng/mL aqueous solution. Various concentrations of analyte solutions were made by dilution of a 3 ng/mL solution for a thorough investigation of selective detection of FQs. A good selective analysis was done by taking 100 \u0026micro;L of TBP stock solution mixed with 2.9 mL (3 ng/mL)of given FQs to make the total volume up to 3 mL. For all luminescent measurements, the photoluminescence spectra were recorded using a spectrofluorometer with λ\u003csub\u003eex\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;353 nm and slit widths of 5 nm and 3 nm for excitation and emission monochromators, respectively.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Synthesis and Characterization of Terbium MOF (TBP)\u003c/h2\u003e \u003cp\u003eTBP was synthesized using the diffusion technique with an equimolar amount of terbium nitrate pentahydrate and BTC (with an excess of pyridine). Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e depicts the overall synthesis process.\u003c/p\u003e \u003cdiv id=\"Sec9\" class=\"Section3\"\u003e \u003ch2\u003e3.1.1. FT-IR\u003c/h2\u003e \u003cp\u003eThe presence of functional groups in TBP was confirmed using FT-IR determinations as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The characteristic bands have been observed for pyridine i.e., 1437, and 1581 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponding to C\u0026thinsp;=\u0026thinsp;N and C\u0026thinsp;=\u0026thinsp;C respectively. BTC has shown broad stretch for O-H at 2843 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and other stretching bands at 1694, and 1267 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e resultant to the carbonyl of carboxylic acid and C-O in that order. Moreover, some new stretching bands have been found in TBP i.e. 1610\u0026thinsp;\u0026minus;\u0026thinsp;1553, 1434\u0026thinsp;\u0026minus;\u0026thinsp;1370, 511, and 457 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e belong to the stretching of the asymmetric and symmetric carboxylic groups, C\u0026thinsp;=\u0026thinsp;N, Tb-O, and Tb-N respectively. Absence of two major stretching bands in pyridine and BTC i.e. Tb-O, and Tb-N but present in TBP confirms the appropriate bonding of both ligands with Tb\u003csup\u003e3+\u003c/sup\u003e in TBP. Such types of stretching frequencies have confirmed the formation of TBP.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section3\"\u003e \u003ch2\u003e3.1.2. PXRD\u003c/h2\u003e \u003cp\u003eFor crystallographic investigation of TBP under the current experimental system, PXRD was performed (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). In comparison to the relative positions of the peaks, the diffraction peaks observed for synthesized TBP at the \u003cem\u003e2\u003c/em\u003eθ scale matched closely with the standard diffraction pattern obtained for the Tb-MOF synthesized by stirring method (Bhardwaj et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). This result reveals that the TBP synthesis was successful. Moreover, the crystalline nature of TBP was also examined with the help of PXRD. The recorded PXRD diffractograms showed sharp peaks at 9.98, 10.26, 13.52, 17.45, 17.96, 20.56, and 31.09 having miller indices (100), (010), (001), (110), (101), (111), and (210) respectively which demonstrated the crystalline structure of the synthesized TBP. The average size (D) of the crystalline sample was estimated with the help of the Debye-Scherrer equation (\u003cb\u003eD\u0026thinsp;=\u0026thinsp;λK/ βcosθ\u003c/b\u003e, where K is the shape factor having value 0.89, λ denotes the X-ray wavelength having value 0.15406 nm, \u003cem\u003eβ\u003c/em\u003eis full width at half maxima (FWHM) and\u003cem\u003eθ\u003c/em\u003edenotes the Bragg\u0026rsquo;s diffraction angle) and it was found to be 46.26 nm.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section3\"\u003e \u003ch2\u003e3.1.3. TGA\u003c/h2\u003e \u003cp\u003eThe TGA was applied to examine the thermal stability of the synthesized TBP (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). According to the first resulting curve, approximately 21.97% mass reduction occurred in the range of 50\u0026ndash;115\u0026deg;C, which is related to processes of dehydration and de-solvation. It implies that in the previously mentioned range of temperature, the TBP loses the solvent moieties located in the pores. The next thermal curve after 465\u0026deg;Cresults from the collapse of the entire framework and the breakdown of the organic ligands. So, TBP was found to exist until 465\u0026deg;C, after that a fast weight reduction of approximately 42.03% occurred, indicating the breakdown of the TBP structure.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section3\"\u003e \u003ch2\u003e3.1.4. FE-SEM\u003c/h2\u003e \u003cp\u003eThe topographical and structural morphology of the TBP was studied by FE-SEM. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e depicted FE-SEM micrographs of TBP at resolutions of x20,000, x40,000, x60,000, and x80,000. The synthesized TBP has shown a rod-shaped morphology, according to these micrographs.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section3\"\u003e \u003ch2\u003e3.1.5. EDX\u003c/h2\u003e \u003cp\u003eThe existence of carbon (C), nitrogen (N), oxygen (O), and terbium (Tb) in TBP was revealed by compositional analysis of EDX spectra, with detected weights (atomic ratios) of 42.80% (63.28%), 2.17% (2.75%), 27.87% (30.93%), and 27.16% (3.03%), respectively (Figure S1). EDX investigation confirmed the high-purity MOF formation by demonstrating the existence of organic ligands and metal elements (O, C, N, and Tb) in the final structure of the TBP.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Detection of fluoroquinolones\u003c/h2\u003e \u003cdiv id=\"Sec15\" class=\"Section3\"\u003e \u003ch2\u003e3.2.1. Selectivity of TBP towards DANO\u003c/h2\u003e \u003cp\u003eWater was chosen as the solvent to examine the fluorescent sensing properties of TBP toward various FQs because TBP has good dispersion, high stability, and photoluminescent features in the aqueous medium. The spectra of PL emission of TBP dispersed in an aqueous medium were recorded at various excitations ranging from 323 nm to 383 nm (Figure S2). The maximum intensity of fluorescence emission was observed at λ\u003csub\u003eex\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;353 nm. As a result, the excitation wavelength at 353 nm was chosen as the best excitation wavelength for further fluorescence studies to detect FQs. For selective analysis, the PL emission spectra of all suspensions (TBP/analyte) were observed and compared (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e And Figure S3). The outcomes showed that each of the FQs under investigation enhanced the intensity of MOF. It is important to note that although other FQs exhibited a slight to moderate enhancement effect on fluorescence intensity, the contact between DANO and TBP significantly enhanced the luminescence. These results indicate that the TBP selectively detects DANO in an aqueous solution.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section3\"\u003e \u003ch2\u003e3.2.2. Sensitivity toward DANO\u003c/h2\u003e \u003cp\u003eTBP sensitivity to DANO was investigated by measuring the effect of DANO on PL emission intensity at λ\u003csub\u003eex\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;353 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e). Remarkably, PL emission increased with increasing DANO concentration. The Stern-Volmer (SV) equation reveals a linear relation between analyte molar concentration (C) and relative luminescent emission intensity (RI) (Qu et al. \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). In this case, It can be properly described as RI-1\u0026thinsp;=\u0026thinsp;K\u003csub\u003eSV\u003c/sub\u003e\u0026times;[C], where RI represents relative intensity expressed by I/I\u003csub\u003eo\u003c/sub\u003e for enhancement, and I\u003csub\u003eo\u003c/sub\u003e/I for quenching. I\u003csub\u003eo\u003c/sub\u003e and I represent the intensity values of photoluminescence emission for TBP before and after the addition of DANO, and Ksv denotes the Stern-Volmer constant (M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). Up to 3 ng/mL (8.40 nM), the SV plot of TBP towards DANO was observed to be linear (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e). The LOD of TBP for DANO in an aqueous medium was determined to be 0.45 ng/mL (1.25 nM) considering the standard deviations (SD) measured using thrice frequent photoluminescence emission study of blank solutions.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section3\"\u003e \u003ch2\u003e3.2.3. Recyclability\u003c/h2\u003e \u003cp\u003eRecyclability is a crucial concern for sensors. So, it also looked at the PL emission characteristics of recovered TBP. It was found that the enhancement in TBP emission intensity following the addition of DANO remained essentially unchanged up to the third recycling cycle, demonstrating its significant value in sensing. The PXRD pattern and FT-IR of TBP were not altered by DANO addition (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e). These results revealed that interactions between DANO and TBP could produce the enhancement phenomenon, but these interactions were not powerful enough to destabilize the crystalline structure of TBP.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec18\" class=\"Section3\"\u003e \u003ch2\u003e3.2.4. The Effect of pH and response time\u003c/h2\u003e \u003cp\u003eUsing hydrochloric acid (0.1 M), and sodium hydroxide (0.1 M)solutions, the PL intensity of the system was calculated in the pH range of 5 to 9, and it was found that the operation is pH-dependent (Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e(A)). In solutions of acidic and basic media, it was discovered that the fluorescence intensity of DANO was lower. The highest fluorescence emission intensity was seen when DANO was added at 7 pH. So, pH 7 was chosen as the optimum pH for further investigation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe emission spectra of TBP-DANO suspension were monitored at intervals of 1 minute up to 10 minutes following excitation at 353 nm to carry out the time-dependent detection of DANO. Figure\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e(B) shows that after 1 minute, the fluorescence emission attained a constant value. The fluorescence emission intensity of the suspension remained nearly unchanged throughout the contact time between DANO and TBP, indicating that the DANO-induced fluorescence enhancement happened relatively fast.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec19\" class=\"Section3\"\u003e \u003ch2\u003e3.2.5. Mechanism\u003c/h2\u003e \u003cp\u003eThe interactions between MOF and analytes were studied to obtain a better knowledge of the detailed mechanism of turn-on fluorescence enhancement behaviour of TBP after the addition of FQs. Possible mechanisms of turn-on enhancement between TBP and DANO are (1) hydrogen bonding interactions and (2) Photo-induced electron transfer (PET).\u003c/p\u003e \u003cp\u003eThe presence of pyridine results in a large surface area of TBP and the probe contains a lot of hydroxyl and carboxyl groups, which allows it to make hydrogen bonds with DANO. Unique and effectual hydrogen-bond may be formed between the (1\u0026prime;s,4\u0026prime;s)-5\u0026prime;-Methyl-2\u0026prime;,5\u0026prime; diazabicyclo[2.2.1]hept-2\u0026prime;-yl ring, hydroxyl, carboxyl, or fluorine of DANO and the carboxyl or hydroxyl groups of TBP (Figure S4). The fluorescence intensity of TBP with DANO was significantly increased under the same excitation. The synergistic effect of hydrogen bonding can aid in the development of larger fluorophores and chromophores (Hua et al. 2018). Further, it can explain the enhancement phenomenon for other FQs (LEVO, OFLO, NOR, and CIPRO) with the same mechanism as the similar hydrogen interactions are present in the case of each analyte, due to which it is difficult to justify different significant enhancement behaviour of DANO. Therefore, the outcomes recommend that only hydrogen bond interactions cannot completely justify the observed enhancement behaviour. Moreover, The PET mechanism may be recognized for the process of enhancement.\u003c/p\u003e \u003cp\u003eAn effective electron transfer between the MOF and analyte is required for PET to function. As it has been proposed for many other MOFs, the PET could govern extremely selective identification of FQs by the TBP. The turn-on enhancement resulted from the transfer of electrons from the E\u003csub\u003eLUMO\u003c/sub\u003e of analytes to the conduction band of TBP when photoexcited because the E\u003csub\u003eLUMO\u003c/sub\u003e of FQs (analytes) were higher than the E\u003csub\u003eLUMO\u003c/sub\u003e of TBP (Figure S5) (Li, Long, et al. 2020). The E\u003csub\u003eHOMO\u003c/sub\u003e and E\u003csub\u003eLUMO\u003c/sub\u003e energies of FQs and BTC were calculated using the Gaussian 09 package programme (Density-functional theory (DFT) study) by taking the basis set B3LYP/6-311G to verify the mechanism related to this turn-on enhancement (Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e). The Frontier Molecular Orbital (FMO) theory established the existence of an easy transfer of electrons between E\u003csub\u003eHOMO\u003c/sub\u003e and E\u003csub\u003eLUMO\u003c/sub\u003e of reacting species. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e, the difference between E\u003csub\u003eLUMO\u003c/sub\u003e of BTC and E\u003csub\u003eLUMO\u003c/sub\u003e of DANO was found to be less than that of other FQs, allowing electrons to easily transfer from E\u003csub\u003eLUMO\u003c/sub\u003e of DANO to E\u003csub\u003eLUMO\u003c/sub\u003e of TBP. This agrees well with the noted highest enhancement for TBP with DANO. This implies that the electron transfer process and H-bonding interactions interact to produce the observed enhancement response.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eThe Tb (III)-based MOF (TBP) has been synthesized using a facile diffusion technique at room temperature under normal conditions for the selective detection of DANO. Structural stability of the synthesized TBP was demonstrated by its ability to be recycled.As TBP has fluorescence properties and remarkable water stability, an excellent approach for fluorescence detection of DANO in water has been developed by utilizing its features. Results indicate that TBP detects DANO specifically in an aqueous medium by producing a significant turn-on enhancement response with the LOD as low as 0.45 ng/mL (1.25 nM).The existence of hydrogen bonding and Photo-induced electron transfer between the TBP and DANO can be linked to the highest turn-on enhancement. The demonstration of the sensor for FQs detection in actual environmental and biological samples may fall under the purview of the expanded scope of this work.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eOne of the authors, Gurdeep Singh, is grateful to University Grants Commission (UGC), New Delhi, India, for providing a junior research fellowship. We are highly thankful to RSIC, Panjab University, Chandigarh, and the Department of Chemistry, Punjabi University, Patiala for spectroscopic analysis.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics approval\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThere is no ethical approval required.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to participate\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll authors give consent to participate in the revision of the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to publish\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll authors give consent to publish the paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor Contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eGurdeep Singh and Deepika Garg has performed the experiment and written the paper. Sanjay Kumar, Rajpal Vermaand has \u0026nbsp;written and edited the paper. All authors reviewed the manuscript.Ashok Kumar Malik has supervised the whole work.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNo Funding available to support this work.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting Interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u0026ldquo;The authors have no relevant financial or non-financial interests to disclose.\u0026rdquo;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability of Data and materials\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll relevant data will be provided on request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAchmann S, Hagen G, Kita J, Malkowsky IM, Kiener C, Ralf Moos (2009) Metal-organic frameworks for sensing applications in the gas phase. 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Inorg Chem Front 7:1161\u0026ndash;1171\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Scheme ","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"environmental-science-and-pollution-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"espr","sideBox":"Learn more about [Environmental Science and Pollution Research](https://www.springer.com/journal/11356)","snPcode":"11356","submissionUrl":"https://submission.nature.com/new-submission/11356/3","title":"Environmental Science and Pollution Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Metal organic framework (MOF), Morphology, Fluoroquinolone Antibiotics (FQs), Fluorescence sensing, Danofloxacin (DANO), Turn-on enhancement","lastPublishedDoi":"10.21203/rs.3.rs-2684011/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-2684011/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA water-dispersible Tb(III)-based Metal Organic Framework (TBP) has been produced by diffusion technique using benzene-1,3,5-tricarboxylic acid (BTC) and pyridine as ligands at low-cost and accessible starting materials. The thermal stability, crystalline nature, and rod-shaped morphology of the synthesized TBP have been confirmed by thermogravimetric (TGA), crystallographic (PXRD), and morphological (FE-SEM) studies. Various spectroscopic techniques have been carried out for detailed qualitative, quantitative, and photoluminescence (PL) analyses. For the quick and precise identification of Danofloxacin (DANO), TBP can be used as a sensor in an aqueous medium with significant enhancement compared to various fluoroquinolone antibiotics (levofloxacin (LEVO), ofloxacin (OFLO), norfloxacin (NOR), and ciprofloxacin (CIPRO)) with low detection limit of 0.45 ng/mL (1.25 nM).According to in-depth mechanistic studies of the density functional theory (DFT) calculations and mode of action, hydrogen bonding interactions and photo-induced electron transfer (PET) are the major factors for turn-on enhancement behaviour of TBP to DANO. The advantages of TBP include simple recovery and reuse for at least three cycles without noticeable loss of sensitivity. All of these characteristics profoundly show how beneficial the detection of DANO in aqueous environments is for the security and safety of the public.\u003c/p\u003e","manuscriptTitle":"Terbium-Based Dual-Ligand Metal Organic Framework by Diffusion Method for Selective and Sensitive Detection of Danofloxacin in Aqueous Medium","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-04-27 13:46:24","doi":"10.21203/rs.3.rs-2684011/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Major Revision","date":"2023-06-19T14:18:08+00:00","index":"","fulltext":""},{"type":"reviewerAgreed","content":"","date":"2023-04-30T19:02:34+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2023-04-24T16:30:50+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"Environmental Science and Pollution Research","date":"2023-04-24T12:39:11+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2023-04-13T05:53:29+00:00","index":"","fulltext":""},{"type":"submitted","content":"Environmental Science and Pollution Research","date":"2023-04-04T03:59:51+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"environmental-science-and-pollution-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"espr","sideBox":"Learn more about [Environmental Science and Pollution Research](https://www.springer.com/journal/11356)","snPcode":"11356","submissionUrl":"https://submission.nature.com/new-submission/11356/3","title":"Environmental Science and Pollution Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"2e7c94f8-67ee-4ebb-850f-31dfd90fdbc7","owner":[],"postedDate":"April 27th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2023-09-25T15:03:54+00:00","versionOfRecord":{"articleIdentity":"rs-2684011","link":"https://doi.org/10.1007/s11356-023-29895-7","journal":{"identity":"environmental-science-and-pollution-research","isVorOnly":false,"title":"Environmental Science and Pollution Research"},"publishedOn":"2023-09-18 15:01:18","publishedOnDateReadable":"September 18th, 2023"},"versionCreatedAt":"2023-04-27 13:46:24","video":"","vorDoi":"10.1007/s11356-023-29895-7","vorDoiUrl":"https://doi.org/10.1007/s11356-023-29895-7","workflowStages":[]},"version":"v1","identity":"rs-2684011","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-2684011","identity":"rs-2684011","version":["v1"]},"buildId":"cBFmMYwuxLRRLfASyISRj","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}