Highly Selective and Sensitive Detection of Quinolone Antibiotics Using Lanthanide Metal-Organic Framework-Based White-Light Materials

Highly Selective and Sensitive Detection of Quinolone Antibiotics Using Lanthanide Metal-Organic Framework-Based White-Light Materials | 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 Highly Selective and Sensitive Detection of Quinolone Antibiotics Using Lanthanide Metal-Organic Framework-Based White-Light Materials Lina Zhao, Guangming Li, Hongbo Liu, Ming Xia This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5328418/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Antibiotics have emerged as predominant contaminants in wastewater, posing significant threats to ecosystems and public health. Consequently, the detection of these antibiotic residues is imperative for mitigating environmental pollution and ensuring food safety. Metal-organic frameworks, characterized by their distinctive structures and optical properties, present innovative solutions for the efficient and sensitive detection of antibiotics. In this study, two lanthanide-based MOF luminophores were synthesized, and by fine-tuning their proportions, white light-emitting materials were developed for the detection of quinolone antibiotics. These luminophores exhibit antibiotic detection through observable colorimetric changes, achieving detection limits as low as 4.863 × 10⁻⁸ M for ciprofloxacin (CPFX) and 9.259 × 10⁻⁷ M for norfloxacin (NFX). This research lays a substantial foundation for the development of high-performance sensors, thereby advancing the field of environmental monitoring technologies. fluorescence detection antibiotics white light materials Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction Quinolone antibiotics constitute a class of antimicrobial agents extensively employed in clinical and veterinary practices, attributed to their broad-spectrum antibacterial efficacy and superior pharmacokinetic properties[ 1 – 4 ]. Nonetheless, the indiscriminate and improper use of quinolone antibiotics has engendered significant public health concerns and environmental hazards[ 5 , 6 ]. The environmental persistence of quinolone antibiotics has become increasingly problematic, as these compounds infiltrate soil and aquatic systems through agricultural, livestock, and aquaculture activities, thereby disrupting ecological equilibrium and posing potential threats to human health via the food chain[ 7 ]. Consequently, the development of efficacious, sensitive, and reliable detection methodologies is of paramount importance for the surveillance and regulation of quinolone antibiotic usage and residues[ 8 , 9 ]. Currently, the detection methodologies for quinolone antibiotics predominantly encompass high-performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS), enzyme-linked immunosorbent assay (ELISA), and electrochemical sensors[ 10 – 13 ]. Nevertheless, these techniques are frequently intricate, necessitating labor-intensive sample preparation, costly instrumentation, and specialized technical expertise, thereby incurring substantial expenses. Consequently, there is a pressing need for the development of novel, efficient, and cost-effective detection materials that are amenable to complex matrices[ 14 ]. Lanthanide metal-organic frameworks (Ln-MOFs) offer significant advantages in sensor applications, especially for antibiotic detection[ 15 – 18 ]. Ln-MOFs combine the unique optical properties of lanthanide ions with the versatile design of organic ligands, providing sensitive and selective detection methods. They feature highly ordered pore structures and large specific surface areas, facilitating efficient capture and recognition of target molecules. These structural attributes enhance detection efficacy by increasing contact area and ensuring rapid molecular transport. The optical properties of lanthanide ions, such as strong fluorescence emission and long luminescence lifetimes, significantly boost detection sensitivity and selectivity[ 19 ].For example, europium (Eu) and terbium (Tb) ions, when incorporated into MOFs, amplify fluorescence signals, improving sensitivity[ 20 ].By selecting different lanthanide ions and organic ligands, the fluorescence properties of Ln-MOFs can be precisely tuned for highly selective detection of specific molecules[ 21 ].Adjusting the emission spectra of Eu and Tb complexes to achieve white light emission further enhances sensitivity and reduces background interference[ 22 ].These attributes make Ln-MOFs particularly advantageous for practical applications. In conclusion, we synthesized Ln-MOFs using Tb and Eu metals with 4,4'-biphenyldicarboxylic acid (BPDC) ligands as sensor materials. By optimizing the doping ratios, we developed white light-emitting materials with enhanced fluorescence response for highly selective antibiotic detection. The sensor demonstrated remarkable sensitivity, rapid response, and low detection limits for quinolone antibiotics, with limits as low as 4.863×10 − 8 M for CPFX and 9.259×10 − 7 M for NFX. These findings lay a strong foundation for advancing novel, efficient sensing technologies. 2. EXPERIMENTAL 2.1 Materials and instrumentation All chemicals and reagents were sourced from HWRK CHEMICALS without further purification. PXRD patterns were obtained using a Rigaku D/Max-3B X-ray diffractometer with Cu Kα radiation (λ = 1.5406 Å) and a graphite monochromator, covering 5° to 45°. UV-Vis absorption spectra were recorded on a PerkinElmer Lambda 35 spectrophotometer over 200 − 700 nm. FT-IR spectra were recorded from 4000 to 500 cm − 1 using a PerkinElmer Spectrum 100 spectrophotometer with KBr. Photoluminescence spectra were obtained using an FLS 1000 Edinburgh fluorescence spectrometer and a PerkinElmer FL 6500 spectrophotometer. Fluorescence lifetimes were measured at room temperature using a single photon counting spectrometer with a microsecond pulsed lamp. 2.2 Synthesis of Tb-BPDC and Eu-BPDC Ln(NO 3 ) 3 ·6H 2 O (0.20 mmol) and biphenyl-4,4'-dicarboxylic acid (0.5 mmol) were added to 12 mL of a H 2 O-DMF (1:4) solvent mixture and stirred for 60 minutes. The solution was transferred to a 25 mL PTFE-lined autoclave, sealed, and heated at 140°C for 72 hours. It was then cooled to room temperature at 0.1°C/min. Crystals were collected by filtration, washed with ethanol and water, and air-dried. The yield was 64%. 2.3 Sensing Method At room temperature, 100 mg of Tb-BPDC and Eu-BPDC were dispersed in 100 mL of distilled water and sonicated at 720 W for 1 hour to prepare a 1 g/L suspension. For selectivity experiments, 1 mL of this suspension was mixed with 1 mL of a 10 mmol antibiotic solution. Luminescence spectra were measured before and after adding analytes, with each experiment repeated three times. For sensitivity measurements, antibiotics were gradually added for luminescence titration. In interference experiments, 1 mL of the suspension was mixed with 1 mL of the interfering substance solution, and emission intensity was measured before and after mixing under 330 nm UV excitation. Then, 1 mL of 10 mmol CPFX and NFX solutions were added, and emission intensity was recorded after each addition. 3. RESULTS AND DISCUSSION 3.1Material Preparation, Structure, and Photophysical Properties Following the literature method, we successfully synthesized the three-dimensional framework structures of Tb-BPDC and Eu-BPDC[ 23 ].As shown in Fig. 1 a, the unit cells of these materials contain a crystallographic ally independent Ln 3+ ion, a BPDC ligand, and a half-protonated dimethylamine molecule. The Ln center is coordinated by eight oxygen atoms from 6 BPDC ligands, forming a distorted [TbO 8 ] polyhedron. To confirm the chemical composition and interactions, infrared spectroscopy was conducted. The IR spectra (Fig. 1 b) show broad N − H stretching bands around 3130 and 3400 cm − 1 , confirming the presence of dimethylamine, sharp peaks between 1400 and 1650 cm − 1 attributed to the carboxylate (C = O) 2 stretching of the BPDC 2− ligand, and a peak at 770 cm − 1 associated with the C − H deformation of 1,4-disubstituted aromatic compounds. Subsequent XRD analysis (Fig. 1 c-d) confirmed the isostructural nature of Tb-BPDC and Eu-BPDC, verifying their crystal structures. To further investigate the optical properties of the materials, UV spectroscopy was performed. The absorption peak at 290 nm in the UV spectra (Fig. 1 e) supports the material characteristics, indicating potential applications in energy transfer. At ambient temperature, we examined the photoluminescence (PL) properties of solid-state Tb-BPDC and Eu-BPDC (Fig. 2 a-b). Specifically, Tb-BPDC exhibited green emission under 316 nm excitation, with emission peaks at 491, 545, 585, and 621 nm, corresponding to the 5 D 4 → 7 F J (J = 6, 5, 4, 3) transitions of Tb³⁺[ 24 ].Notably, the 5 D 4 → 7 F 5 transition was the most intense, indicating that the antenna effect of the framework significantly enhanced energy transfer from the ligand to Tb³⁺[ 25 ].Conversely, Eu-BPDC demonstrated strong luminescence in the red-orange region, primarily attributed to the 5 D 0 → 7 F J (J = 1, 2, 4) transitions. The 5 D 0 → 7 F 2 transition was particularly prominent and sensitive, whereas the 5 D 0 → 7 F 3 transition at 660 nm was comparatively weaker. These properties underscore the distinctive luminescent behavior of the Eu complex. The lifetime of Tb-BPDC was determined to be 193.58 µs (Fig. 2 c), with its luminescence mechanism depicted in Fig. 2 d. By fine-tuning the ratio of Tb to Eu, we successfully synthesized white-light-emitting composites, thereby enhancing their potential for diverse applications. To assess practical reliability, we evaluated the fluorescence stability of the materials (Fig. 3 a-c). The results showed stable fluorescence over 0–18 hours and robust stability under near-neutral pH and varying temperatures, confirming their suitability for diverse environments. 3.2 Fluorescence Sensing We evaluated the fluorescence sensing capabilities of the white-light materials for detecting thirteen common antibiotics (SDZ, FZD, SMZ, THZ, ACL, DCL, CFX, KNM, ROX, AZM, CPFX, NFX, LCC) using a 1 g/L aqueous suspension as the sensor. Incremental addition of 0.01 M antibiotic solutions showed that the sensor had a significant fluorescent response to quinolone antibiotics, with the emission color changing from white to blue, while showing no significant change for other antibiotics (Fig. 3 a). These findings demonstrate the responsiveness of the white-light material to quinolone antibiotics. Subsequent luminescence titration experiments (Fig. 3 b-c) revealed that increasing concentrations of quinolone antibiotics resulted in a marked enhancement of fluorescence intensity at 450 nm, with blue emission progressively dominating. The parameter I/I 0 − 1 was calculated, where I 0 and I represent the fluorescence intensities in the absence and presence of quinolone antibiotics, respectively[ 26 ]. Thereafter, a Stern-Volmer (SV) plot (Fig. 3 e and f) was generated to elucidate the relationship between the quinolone antibiotic concentration ([C]) and the enhancement efficiency ( I/I 0 − 1 ). The SV plot exhibited a robust double-logarithmic linear correlation, with an R 2 value of 0.99. In the SV equation ( I/I 0 − 1 = K SV [ C ]), the calculated K SV values were 6.17×105M − 1 for CPFX and 3.24×104 M − 1 for NFX. The limit of detection (LOD) was determined using 3σ/K SV , yielding LODs of 4.863×10 − 8 M for CPFX and 9.259×10 − 7 M for NFX, where σ denotes the standard deviation of the blank sample's intensity at 450 nm, based on at least three independent measurements. Finally, to validate the selectivity of the white-light material under complex conditions, we performed interference tests. The sensor exhibited robust detection performance for quinolone antibiotics even in the presence of other antibiotic interferents. This underscores its exceptional selectivity and sensitivity in the detection of quinolone antibiotics. 3.3 Mechanism analysis The proposed mechanism involves energy distribution and transfer processes, including Förster resonance energy transfer (FRET) and the inner filter effect (IFE)[ 27 – 29 ].Given the limited overlap between the UV-visible absorption spectra of the antibiotics and the emission spectrum of the sensor, FRET is unlikely to occur (Fig. 6 a). Conversely, the inner filter effect is pivotal in the sensing process. Specifically, NFX and CPFX exhibit substantial absorption in the 300–390 nm range. These antibiotics absorb the emitted light from the sensor and subsequently re-emit blue light, resulting in a change in the emission color (Fig. 6 b). This phenomenon effectively elucidates the fluorescence color change induced by quinolones, highlighting the inner filter effect as a crucial factor in the sensor's sensitivity. 4. Conclusion In this study, we synthesized Tb-BPDC and Eu-BPDC and investigated their potential for detecting quinolone antibiotics, focusing on selectivity and sensitivity. The materials exhibited exceptional performance in detecting NFX and CPFX, highlighting their high-efficiency fluorescence sensing capabilities. This research lays a foundation for novel chemical sensors, enabling applications in complex environments and supporting advancements in environmental monitoring and public health. Continuous optimization and innovation could lead to breakthroughs in practical applications, meeting the demand for advanced detection solutions. Declarations CONFLICT OF INTEREST STATEMENT The authors declare that there are no conflicts of interest. Author Contribution L.Zhao and M Xia wrote the main manuscript text and prepared all figures. All authors reviewed the manuscript. ACKNOWLEDGMENTS This study was supported by the National Natural Science Foundation of China (22309046), Heilongjiang Province Double First-Class Disciplines Collaborative Innovation Achievement Project (LJGXCG2023-085 and LJGXCG2024-F12), Postdoctoral Research Grant of Heilongjiang Province (LBH-Z23265), and Key Projects of Heilongjiang Province (GZ20220162). DATA AVAILABILITY STATEMENT The data that support the findings of this study are available on request from the corresponding author. The data are not publicly available due to privacy or ethical restrictions. References T.D.M. Pham, Z.M. Ziora, M.A.T. 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Growth Des. 19 , 4854 (2019) I.N. Hegarty, S.J. Bradberry, J.I. Lovitt, J.M. Delente, N. Willis-Fox, R. Daly, T. Gunnlaugsson, Mater. Chem. Front. 7 , 906 (2023) M. Shen, B. Liu, L. Xu, H. Jiao, J. Mater. Chem. C 8 , 4392 (2020) Y. Yang, L. Zhao, M. Sun, P. Wei, G. Li, Y. Li, Dyes Pigm. 180 , 108444 (2020) X. Feng, Y. Shang, K. Zhang, M. Hong, J. Li, H. Xu, L. Wang, Z. Li, CrystEngComm 2022, 24 , 4187 R. Laishram, U. Maitra, Chem. Commun. 58 , 3162 (2022) J. Ran, L. Yang, C. Liu, Q. Liu, Y. Liu, S. Li, Y. Fu, F. Ye, Sci. Total Environ. 931 , 172866 (2024) Additional Declarations No competing interests reported. Cite Share Download PDF Status: Posted Version 1 posted 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. 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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-5328418","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":370489096,"identity":"b8d116bb-c4de-4dd3-9fdd-3a5f1309fca4","order_by":0,"name":"Lina Zhao","email":"","orcid":"","institution":"Heilongjiang University","correspondingAuthor":false,"prefix":"","firstName":"Lina","middleName":"","lastName":"Zhao","suffix":""},{"id":370489097,"identity":"e3312af3-6d22-4006-b578-f3c25b4b3ae7","order_by":1,"name":"Guangming Li","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAuElEQVRIiWNgGAWjYFAC5oYDHxssmEFMCSK1MDYcnNkgQaIWZt4GiGLitMiHHWw8bLtDgt3gAPPB2zwMdnkEtRjeTmw4nHtGgtngAFuyNQ9DcjFhLbNBWtpAWnjMpHkYDiQ2EKXFEqyF/xtxWuSlgVoYIbawEafFAKjlYC9Qi+RhNmPLOQbJRNgyO/nwh59tNsl8x5sf3nhTYUeELQcgdDIDODINCKkH2QI11I4ItaNgFIyCUTBSAQAFzTpNXjTLgwAAAABJRU5ErkJggg==","orcid":"","institution":"Heilongjiang University","correspondingAuthor":true,"prefix":"","firstName":"Guangming","middleName":"","lastName":"Li","suffix":""},{"id":370489098,"identity":"32f5090c-bff1-49fc-a038-1b7560a5d149","order_by":2,"name":"Hongbo Liu","email":"","orcid":"","institution":"Heilongjiang University","correspondingAuthor":false,"prefix":"","firstName":"Hongbo","middleName":"","lastName":"Liu","suffix":""},{"id":370489099,"identity":"6c141cb8-726e-4733-a704-fd07c647b865","order_by":3,"name":"Ming Xia","email":"","orcid":"","institution":"Heilongjiang University","correspondingAuthor":false,"prefix":"","firstName":"Ming","middleName":"","lastName":"Xia","suffix":""}],"badges":[],"createdAt":"2024-10-24 22:23:07","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5328418/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5328418/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":68353448,"identity":"a069ccc7-f603-49b3-ba1f-0968c92f4992","added_by":"auto","created_at":"2024-11-06 11:04:52","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":287067,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Three-dimensional (3D) framework of Tb-BPDC and Eu-BPDC; (b) FT-IR spectra of, Tb-BPDC and Eu-BPDC;(c) PXRD patterns of Tb-BPDC and Eu-BPDC (d);(e) UV-Vis spectra of Tb-BPDC and Eu-BPDC.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-5328418/v1/b53bfc57870b58e94b1f8157.png"},{"id":68355329,"identity":"6e4cb0e8-a988-4527-a380-2627b72c9b23","added_by":"auto","created_at":"2024-11-06 11:20:52","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":248973,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Excitation and emission spectra of Tb-BPDC and Eu-BPDC (b); (c) Luminescent lifetimes of solid-state Tb-BPDC; (d) The energy transfer from BPDC ligands to Tb\u003csup\u003e3+\u003c/sup\u003e and Eu\u003csup\u003e3+\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-5328418/v1/b165c5515473d2e53f94de5c.png"},{"id":68353450,"identity":"df4bcb65-7814-4dc3-a20e-86a0bf986f5c","added_by":"auto","created_at":"2024-11-06 11:04:52","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":129714,"visible":true,"origin":"","legend":"\u003cp\u003e(a)Relationship between luminescence intensity at 545 nm and time; (b) Relationship between luminescence intensity at 545 nm and pH values; (c) Temperature-dependent photoluminescence spectra of white materials.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-5328418/v1/1b8ce3cde920ba919b7d7a8c.png"},{"id":68355015,"identity":"c157eb27-b1c0-4c79-9feb-45b0990ef36a","added_by":"auto","created_at":"2024-11-06 11:12:52","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":279577,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Luminescence spectra of white materials aqueous solution in the absence and presence of various antibiotics; (b) Concentration dependence between white materials and CPFX and NFX (c); (d) CIE diagram of white materials before and after adding CPFX and NFX in water; (e) K\u003csub\u003eSV\u003c/sub\u003e plot of white materials toward CPFX and NFX (f) by monitoring 450 nm.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-5328418/v1/1383c74a6fa1673a67fe9094.png"},{"id":68355016,"identity":"0ed1ded1-4a85-4d46-bb90-cf4cab7c3457","added_by":"auto","created_at":"2024-11-06 11:12:52","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":201911,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Selective competitiveness before and after adding CPFX into the well-dispersed white materials aqueous suspension with other antibiotics; (b) Selective competitiveness before and after adding NFX into the well-dispersed white materials aqueous suspension with other antibiotics.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-5328418/v1/ffc6acb1661dc2ca41d4090c.png"},{"id":68353453,"identity":"a8a8ede0-bb28-4578-a2d7-b9f579b3198e","added_by":"auto","created_at":"2024-11-06 11:04:52","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":185634,"visible":true,"origin":"","legend":"\u003cp\u003e(a) UV-Vis spectra of various antibiotics; (b) Luminescence spectra of various antibiotics.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-5328418/v1/207bb2eb7389938956d71187.png"},{"id":71688927,"identity":"9a10b298-d1e4-4a4c-8928-ee0af2c6352d","added_by":"auto","created_at":"2024-12-17 17:46:55","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1702990,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5328418/v1/098d9e03-8929-4792-b178-4f6ff4070533.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Highly Selective and Sensitive Detection of Quinolone Antibiotics Using Lanthanide Metal-Organic Framework-Based White-Light Materials","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eQuinolone antibiotics constitute a class of antimicrobial agents extensively employed in clinical and veterinary practices, attributed to their broad-spectrum antibacterial efficacy and superior pharmacokinetic properties[\u003cspan additionalcitationids=\"CR2 CR3\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Nonetheless, the indiscriminate and improper use of quinolone antibiotics has engendered significant public health concerns and environmental hazards[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. The environmental persistence of quinolone antibiotics has become increasingly problematic, as these compounds infiltrate soil and aquatic systems through agricultural, livestock, and aquaculture activities, thereby disrupting ecological equilibrium and posing potential threats to human health via the food chain[\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. Consequently, the development of efficacious, sensitive, and reliable detection methodologies is of paramount importance for the surveillance and regulation of quinolone antibiotic usage and residues[\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eCurrently, the detection methodologies for quinolone antibiotics predominantly encompass high-performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS), enzyme-linked immunosorbent assay (ELISA), and electrochemical sensors[\u003cspan additionalcitationids=\"CR11 CR12\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. Nevertheless, these techniques are frequently intricate, necessitating labor-intensive sample preparation, costly instrumentation, and specialized technical expertise, thereby incurring substantial expenses. Consequently, there is a pressing need for the development of novel, efficient, and cost-effective detection materials that are amenable to complex matrices[\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eLanthanide metal-organic frameworks (Ln-MOFs) offer significant advantages in sensor applications, especially for antibiotic detection[\u003cspan additionalcitationids=\"CR16 CR17\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. Ln-MOFs combine the unique optical properties of lanthanide ions with the versatile design of organic ligands, providing sensitive and selective detection methods. They feature highly ordered pore structures and large specific surface areas, facilitating efficient capture and recognition of target molecules. These structural attributes enhance detection efficacy by increasing contact area and ensuring rapid molecular transport. The optical properties of lanthanide ions, such as strong fluorescence emission and long luminescence lifetimes, significantly boost detection sensitivity and selectivity[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e].For example, europium (Eu) and terbium (Tb) ions, when incorporated into MOFs, amplify fluorescence signals, improving sensitivity[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e].By selecting different lanthanide ions and organic ligands, the fluorescence properties of Ln-MOFs can be precisely tuned for highly selective detection of specific molecules[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e].Adjusting the emission spectra of Eu and Tb complexes to achieve white light emission further enhances sensitivity and reduces background interference[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e].These attributes make Ln-MOFs particularly advantageous for practical applications.\u003c/p\u003e \u003cp\u003eIn conclusion, we synthesized Ln-MOFs using Tb and Eu metals with 4,4'-biphenyldicarboxylic acid (BPDC) ligands as sensor materials. By optimizing the doping ratios, we developed white light-emitting materials with enhanced fluorescence response for highly selective antibiotic detection. The sensor demonstrated remarkable sensitivity, rapid response, and low detection limits for quinolone antibiotics, with limits as low as 4.863\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;8\u003c/sup\u003e M for CPFX and 9.259\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;7\u003c/sup\u003e M for NFX. These findings lay a strong foundation for advancing novel, efficient sensing technologies.\u003c/p\u003e"},{"header":"2. EXPERIMENTAL","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials and instrumentation\u003c/h2\u003e \u003cp\u003eAll chemicals and reagents were sourced from HWRK CHEMICALS without further purification. PXRD patterns were obtained using a Rigaku D/Max-3B X-ray diffractometer with Cu Kα radiation (λ\u0026thinsp;=\u0026thinsp;1.5406 \u0026Aring;) and a graphite monochromator, covering 5\u0026deg; to 45\u0026deg;. UV-Vis absorption spectra were recorded on a PerkinElmer Lambda 35 spectrophotometer over 200\u0026thinsp;\u0026minus;\u0026thinsp;700 nm. FT-IR spectra were recorded from 4000 to 500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e using a PerkinElmer Spectrum 100 spectrophotometer with KBr. Photoluminescence spectra were obtained using an FLS 1000 Edinburgh fluorescence spectrometer and a PerkinElmer FL 6500 spectrophotometer. Fluorescence lifetimes were measured at room temperature using a single photon counting spectrometer with a microsecond pulsed lamp.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis of Tb-BPDC and Eu-BPDC\u003c/h2\u003e \u003cp\u003eLn(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO (0.20 mmol) and biphenyl-4,4'-dicarboxylic acid (0.5 mmol) were added to 12 mL of a H\u003csub\u003e2\u003c/sub\u003eO-DMF (1:4) solvent mixture and stirred for 60 minutes. The solution was transferred to a 25 mL PTFE-lined autoclave, sealed, and heated at 140\u0026deg;C for 72 hours. It was then cooled to room temperature at 0.1\u0026deg;C/min. Crystals were collected by filtration, washed with ethanol and water, and air-dried. The yield was 64%.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Sensing Method\u003c/h2\u003e \u003cp\u003eAt room temperature, 100 mg of Tb-BPDC and Eu-BPDC were dispersed in 100 mL of distilled water and sonicated at 720 W for 1 hour to prepare a 1 g/L suspension. For selectivity experiments, 1 mL of this suspension was mixed with 1 mL of a 10 mmol antibiotic solution. Luminescence spectra were measured before and after adding analytes, with each experiment repeated three times. For sensitivity measurements, antibiotics were gradually added for luminescence titration. In interference experiments, 1 mL of the suspension was mixed with 1 mL of the interfering substance solution, and emission intensity was measured before and after mixing under 330 nm UV excitation. Then, 1 mL of 10 mmol CPFX and NFX solutions were added, and emission intensity was recorded after each addition.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. RESULTS AND DISCUSSION","content":"\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.1Material Preparation, Structure, and Photophysical Properties\u003c/h2\u003e \u003cp\u003eFollowing the literature method, we successfully synthesized the three-dimensional framework structures of Tb-BPDC and Eu-BPDC[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e].As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, the unit cells of these materials contain a crystallographic ally independent Ln\u003csup\u003e3+\u003c/sup\u003e ion, a BPDC ligand, and a half-protonated dimethylamine molecule. The Ln center is coordinated by eight oxygen atoms from 6 BPDC ligands, forming a distorted [TbO\u003csub\u003e8\u003c/sub\u003e] polyhedron. To confirm the chemical composition and interactions, infrared spectroscopy was conducted. The IR spectra (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb) show broad N\u0026thinsp;\u0026minus;\u0026thinsp;H stretching bands around 3130 and 3400 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, confirming the presence of dimethylamine, sharp peaks between 1400 and 1650 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e attributed to the carboxylate (C\u0026thinsp;=\u0026thinsp;O)\u003csub\u003e2\u003c/sub\u003e stretching of the BPDC\u003csup\u003e2\u0026minus;\u003c/sup\u003e ligand, and a peak at 770 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e associated with the C\u0026thinsp;\u0026minus;\u0026thinsp;H deformation of 1,4-disubstituted aromatic compounds. Subsequent XRD analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec-d) confirmed the isostructural nature of Tb-BPDC and Eu-BPDC, verifying their crystal structures. To further investigate the optical properties of the materials, UV spectroscopy was performed. The absorption peak at 290 nm in the UV spectra (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ee) supports the material characteristics, indicating potential applications in energy transfer.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAt ambient temperature, we examined the photoluminescence (PL) properties of solid-state Tb-BPDC and Eu-BPDC (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea-b). Specifically, Tb-BPDC exhibited green emission under 316 nm excitation, with emission peaks at 491, 545, 585, and 621 nm, corresponding to the \u003csup\u003e5\u003c/sup\u003eD\u003csub\u003e4\u003c/sub\u003e \u0026rarr; \u003csup\u003e7\u003c/sup\u003eF\u003csub\u003eJ\u003c/sub\u003e (J\u0026thinsp;=\u0026thinsp;6, 5, 4, 3) transitions of Tb\u0026sup3;⁺[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e].Notably, the \u003csup\u003e5\u003c/sup\u003eD\u003csub\u003e4\u003c/sub\u003e \u0026rarr; \u003csup\u003e7\u003c/sup\u003eF\u003csub\u003e5\u003c/sub\u003e transition was the most intense, indicating that the antenna effect of the framework significantly enhanced energy transfer from the ligand to Tb\u0026sup3;⁺[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e].Conversely, Eu-BPDC demonstrated strong luminescence in the red-orange region, primarily attributed to the \u003csup\u003e5\u003c/sup\u003eD\u003csub\u003e0\u003c/sub\u003e \u0026rarr; \u003csup\u003e7\u003c/sup\u003eF\u003csub\u003eJ\u003c/sub\u003e (J\u0026thinsp;=\u0026thinsp;1, 2, 4) transitions. The \u003csup\u003e5\u003c/sup\u003eD\u003csub\u003e0\u003c/sub\u003e \u0026rarr; \u003csup\u003e7\u003c/sup\u003eF\u003csub\u003e2\u003c/sub\u003e transition was particularly prominent and sensitive, whereas the \u003csup\u003e5\u003c/sup\u003eD\u003csub\u003e0\u003c/sub\u003e \u0026rarr; \u003csup\u003e7\u003c/sup\u003eF\u003csub\u003e3\u003c/sub\u003e transition at 660 nm was comparatively weaker. These properties underscore the distinctive luminescent behavior of the Eu complex. The lifetime of Tb-BPDC was determined to be 193.58 \u0026micro;s (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec), with its luminescence mechanism depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed. By fine-tuning the ratio of Tb to Eu, we successfully synthesized white-light-emitting composites, thereby enhancing their potential for diverse applications.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo assess practical reliability, we evaluated the fluorescence stability of the materials (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea-c). The results showed stable fluorescence over 0\u0026ndash;18 hours and robust stability under near-neutral pH and varying temperatures, confirming their suitability for diverse environments.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Fluorescence Sensing\u003c/h2\u003e \u003cp\u003eWe evaluated the fluorescence sensing capabilities of the white-light materials for detecting thirteen common antibiotics (SDZ, FZD, SMZ, THZ, ACL, DCL, CFX, KNM, ROX, AZM, CPFX, NFX, LCC) using a 1 g/L aqueous suspension as the sensor. Incremental addition of 0.01 M antibiotic solutions showed that the sensor had a significant fluorescent response to quinolone antibiotics, with the emission color changing from white to blue, while showing no significant change for other antibiotics (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea).\u003c/p\u003e \u003cp\u003eThese findings demonstrate the responsiveness of the white-light material to quinolone antibiotics. Subsequent luminescence titration experiments (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb-c) revealed that increasing concentrations of quinolone antibiotics resulted in a marked enhancement of fluorescence intensity at 450 nm, with blue emission progressively dominating. The parameter \u003cem\u003eI/I\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;\u003cem\u003e\u0026minus;\u0026thinsp;1\u003c/em\u003e was calculated, where I\u003csub\u003e0\u003c/sub\u003e and I represent the fluorescence intensities in the absence and presence of quinolone antibiotics, respectively[\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Thereafter, a Stern-Volmer (SV) plot (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee and f) was generated to elucidate the relationship between the quinolone antibiotic concentration ([C]) and the enhancement efficiency (\u003cem\u003eI/I\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;\u003cem\u003e\u0026minus;\u0026thinsp;1\u003c/em\u003e). The SV plot exhibited a robust double-logarithmic linear correlation, with an \u003cem\u003eR\u003c/em\u003e\u003csup\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sup\u003e value of 0.99. In the SV equation (\u003cem\u003eI/I\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;1\u0026thinsp;=\u0026thinsp;\u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003eSV\u003c/em\u003e\u003c/sub\u003e[\u003cem\u003eC\u003c/em\u003e]), the calculated \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003eSV\u003c/em\u003e\u003c/sub\u003e values were 6.17\u0026times;105M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for CPFX and 3.24\u0026times;104 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for NFX. The limit of detection (LOD) was determined using \u003cem\u003e3σ/K\u003c/em\u003e\u003csub\u003e\u003cem\u003eSV\u003c/em\u003e\u003c/sub\u003e, yielding LODs of 4.863\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;8\u003c/sup\u003e M for CPFX and 9.259\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;7\u003c/sup\u003e M for NFX, where \u003cem\u003eσ\u003c/em\u003e denotes the standard deviation of the blank sample's intensity at 450 nm, based on at least three independent measurements.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFinally, to validate the selectivity of the white-light material under complex conditions, we performed interference tests. The sensor exhibited robust detection performance for quinolone antibiotics even in the presence of other antibiotic interferents. This underscores its exceptional selectivity and sensitivity in the detection of quinolone antibiotics.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Mechanism analysis\u003c/h2\u003e \u003cp\u003eThe proposed mechanism involves energy distribution and transfer processes, including F\u0026ouml;rster resonance energy transfer (FRET) and the inner filter effect (IFE)[\u003cspan additionalcitationids=\"CR28\" citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].Given the limited overlap between the UV-visible absorption spectra of the antibiotics and the emission spectrum of the sensor, FRET is unlikely to occur (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea). Conversely, the inner filter effect is pivotal in the sensing process. Specifically, NFX and CPFX exhibit substantial absorption in the 300\u0026ndash;390 nm range. These antibiotics absorb the emitted light from the sensor and subsequently re-emit blue light, resulting in a change in the emission color (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb). This phenomenon effectively elucidates the fluorescence color change induced by quinolones, highlighting the inner filter effect as a crucial factor in the sensor's sensitivity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn this study, we synthesized Tb-BPDC and Eu-BPDC and investigated their potential for detecting quinolone antibiotics, focusing on selectivity and sensitivity. The materials exhibited exceptional performance in detecting NFX and CPFX, highlighting their high-efficiency fluorescence sensing capabilities. This research lays a foundation for novel chemical sensors, enabling applications in complex environments and supporting advancements in environmental monitoring and public health. Continuous optimization and innovation could lead to breakthroughs in practical applications, meeting the demand for advanced detection solutions.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eCONFLICT OF INTEREST STATEMENT\u003c/h2\u003e \u003cp\u003eThe authors declare that there are no conflicts of interest.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eL.Zhao and M Xia wrote the main manuscript text and prepared all figures. All authors reviewed the manuscript.\u003c/p\u003e\u003ch2\u003eACKNOWLEDGMENTS\u003c/h2\u003e \u003cp\u003eThis study was supported by the National Natural Science Foundation of China (22309046), Heilongjiang Province Double First-Class Disciplines Collaborative Innovation Achievement Project (LJGXCG2023-085 and LJGXCG2024-F12), Postdoctoral Research Grant of Heilongjiang Province (LBH-Z23265), and Key Projects of Heilongjiang Province (GZ20220162).\u003c/p\u003e\u003ch2\u003eDATA AVAILABILITY STATEMENT\u003c/h2\u003e \u003cp\u003eThe data that support the findings of this study are available on request from the corresponding author. The data are not publicly available due to privacy or ethical restrictions.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eT.D.M. Pham, Z.M. Ziora, M.A.T. 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Total Environ. \u003cb\u003e931\u003c/b\u003e, 172866 (2024)\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"fluorescence detection, antibiotics, white light materials","lastPublishedDoi":"10.21203/rs.3.rs-5328418/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5328418/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eAntibiotics have emerged as predominant contaminants in wastewater, posing significant threats to ecosystems and public health. Consequently, the detection of these antibiotic residues is imperative for mitigating environmental pollution and ensuring food safety. Metal-organic frameworks, characterized by their distinctive structures and optical properties, present innovative solutions for the efficient and sensitive detection of antibiotics. In this study, two lanthanide-based MOF luminophores were synthesized, and by fine-tuning their proportions, white light-emitting materials were developed for the detection of quinolone antibiotics. These luminophores exhibit antibiotic detection through observable colorimetric changes, achieving detection limits as low as 4.863 \u0026times; 10⁻⁸ M for ciprofloxacin (CPFX) and 9.259 \u0026times; 10⁻⁷ M for norfloxacin (NFX). This research lays a substantial foundation for the development of high-performance sensors, thereby advancing the field of environmental monitoring technologies.\u003c/p\u003e","manuscriptTitle":"Highly Selective and Sensitive Detection of Quinolone Antibiotics Using Lanthanide Metal-Organic Framework-Based White-Light Materials","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-11-06 11:04:47","doi":"10.21203/rs.3.rs-5328418/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"ee0e890b-b335-4474-b28b-bb584723d978","owner":[],"postedDate":"November 6th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-12-17T17:38:47+00:00","versionOfRecord":[],"versionCreatedAt":"2024-11-06 11:04:47","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5328418","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5328418","identity":"rs-5328418","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}