Eu-MOF-Based Fluorescent Ratiometric Sensor by Detecting 3,4,5-Trihydroxybenzoic for Fingerprint Visualization on Porous Objects

Abstract

Latent fingerprints (LFPs) at the crime scene are served as important clues to locate the trajectory of criminal behavior and portray the characteristics of the suspect. Therefore, visualizing LFPs is of considerable significance. In this work, the europium metal-organic framework (Eu-MOF) sensor was successfully constructed for sensitive detection of gallic acid (3,4,5-trihydroxybenzoic acid, GA) and visualization of the sweat LFPs. The boric-acid-modified Eu-MOF was prepared by using the simple one-pot solvothermal method using Eu as the metal ion center and 3,5-dicarboxybenzeneboronic acid (BBDC) as the organic ligand. The sensor showed desirable photoluminescent performance through the chelating of BBDC with Eu³⁺. The sensor exhibited the satisfactory linear relationship to GA in the range of 1 nM to 20 nM with a low detection limit of 0.34 nM under the optimized conditions. The prepared sensor with ideal selectivity to GA was successfully applied for visualizing LFPs on porous substrates with the high contrast and superior stability. Given the good performance of the sensor, all fingerprint images obtained from 1 200 samples presented clear friction ridges and met the identification criteria. Notably, the sensor had less impact on the subsequent deoxyribonucleic acid (DNA) detection, displaying a promising perspective for applications in extracting physical evidence of site investigation.

Keywords

Europium metal-organic framework (Eu-MOF) / photoluminescence / 3,4,5-trihydroxybenzoic / latent fingerprints (LFPs) development

References

[[1]] Ulery B T, Hicklin R A, Kiebuzinski G I, Roberts M A, Buscaglia J. Understanding the sufficiency of information for latent fingerprint value determinations. Forensic Science International, 2013, 230(1–3): 99-106,

[[2]] de Ronde A, Kokshoorn B, de Poot C J, de Puit M. The evaluation of fingermarks given activity level propositions. Forensic Science International, 2019, 302: 109904,

[[3]] Sheridan K J, Saltupyte E, Palmer R, Gallidabino M D. A study on contactless airborne transfer of textile fibres between different garments in small compact semi-enclosed spaces. Forensic Science International, 2020, 315: 110432,

[[4]] Bennett S, Roux C P, Robertson J. The significance of fibre transfer and persistence–a case study. Australian Journal of Forensic Sciences, 2010, 42(3): 221-228,

[[5]] Palmer R, Sheridan K, Puckett J, Richardson N, Lo W. An investigation into secondary transfer–the transfer of textile fibres to seats. Forensic Science International, 2017, 278: 334-337,

[[6]] Calderón-Santiago M, Priego-Capote F, Jurado-Gámez B, Luque de Castro M D. Optimization study for metabolomics analysis of human sweat by liquid chromatography-tandem mass spectrometry in high resolution mode. Journal of Chromatography A, 2014, 1333: 70-78,

[[7]] Iglesias J, Medina I, Pazos M, Watson R, Preedy V R, Zibadi S. . Polyphenols in Human Health and Disease, 2014 San Diego Academic Press 323-338,

[[8]] James T D, Sandanayake K R A S, Shinkai S. Saccharide sensing with molecular receptors based on boronic acid. Angewandte Chemie International Edition in English, 1996, 35(17): 1910-1922,

[[9]] Meng S, Li G, Wang P, He M, Sun X, Li Z. Rare earth-based MOFs for photo/electrocatalysis. Materials Chemistry Frontiers, 2023, 7(5): 806-827,

[[10]] Carlos L D, Ferreira R A S, de Z. Bermudez V, Ribeiro S J L. Lanthanide-containing light-emitting organic-inorganic hybrids: a bet on the future. Advanced Materials, 2009, 21(5): 509-534,

[[11]] Lima P P, Almeida Paz F A, Ferreira R A S, de Zea Bermudez V, Carlos L D. Ligand-assisted rational design and supramolecular tectonics toward highly luminescent Eu³⁺-containing organic-inorganic hybrids. Chemistry of Materials, 2009, 21(21): 5099-5111,

[[12]] Ansari A A, Labis J P, Khan A. Facile synthesized NaGdF4:Yb,Er peanut - shaped, highly biocompatible, colloidal upconversion nanospheres. Luminescence, 2022, 37(7): 1048-1056,

[[13]] Yang D, Xu J, Yang G, Zhou Y, Ji H, Bi H, et al.. Metal-organic frameworks join hands to create an anti-cancer nanoplatform based on 808 nm light driving up-conversion nanoparticles. Chemical Engineering Journal, 2018, 344: 363-374,

[[14]] Zhao L, Song X, Ren X, Wang H, Fan D, Wu D, et al.. Ultrasensitive near-infrared electrochemiluminescence biosensor derived from Eu-MOF with antenna effect and high efficiency catalysis of specific CoS₂ hollow triple shelled nanoboxes for procalcitonin. Biosensors and Bioelectronics, 2021, 191: 113409,

[[15]] Song L, Xiao J, Cui R, Wang X, Tian F, Liu Z. Eu³⁺ doped bismuth metal-organic frameworks with ultrahigh fluorescence quantum yield and act as ratiometric turn-on sensor for histidine detection. Sensors and Actuators B: Chemical, 2021, 336: 129753,

[[16]] Wu J, Li Y, Song B, Zhang C, Wang Q, Gao X, et al.. Microstructured optical fiber based on surface plasmon resonance for dual-optofluidic-channel sensing. Plasmonics, 2022, 17(5): 1965-1971,

[[17]] Ben Zakour S, Taleb H. Shift endpoint trace selection algorithm and wavelet analysis to detect the endpoint using optical emission spectroscopy. Photonic Sensors, 2016, 6: 158-168,

[[18]] Pei L, Zhang W, Yang S, Chen K, Zhu X, Zhao Y, et al.. Nitrogen and sulfur Co-doped carbon dots as a turn-off fluorescence probe for the detection of cerium and iron. Journal of Fluorescence, 2023, 33(3): 1147-1156,

[[19]] Qiao X, Han Y, Tian D, Yang Z, Li J, Zhao S. MOF matrix doped with rare earth ions to realize ratiometric fluorescent sensing of 2,4,6-trinitrophenol: synthesis, characterization and performance. Sensors and Actuators B: Chemical, 2019, 286: 1-8,

[[20]] Jiang X, Jin H, Sun Y, Sun Z, Gui R. Assembly of black phosphorus quantum dots-doped MOF and silver nanoclusters as a versatile enzyme-catalyzed biosensor for solution, flexible substrate and latent fingerprint visual detection of baicalin. Biosensors and Bioelectronics, 2020, 152: 112012,

[[21]] Sun L, Zhang Y, Lv X S, Li H D. A luminescent Eu-based MOFs material for the sensitive detection of nitro explosives and development of fingerprint. Inorganic Chemistry Communications, 2023, 156: 111267,

[[22]] Sun Z, Li Y, Ma Y, Li L. Dual-functional recyclable luminescent sensors based on 2D lanthanide-based metal-organic frameworks for highly sensitive detection of Fe³⁺ and 2,4-dinitrophenol. Dyes and Pigments, 2017, 146: 263-271,

[[23]] Cui Y, Chen F, Yin X B. A ratiometric fluorescence platform based on boric-acid-functional Eu-MOF for sensitive detection of H₂O₂ and glucose. Biosensors and Bioelectronics, 2019, 135: 208-215,

[[24]] Fitzpatrick L R, Woldemariam T. . Comprehensive Medicinal Chemistry III, 2017 Berlin Elsevier 495-510,

[[25]] Li J, Yang Y, Li Y, Zhao P, Fei J, Xie Y. Detection of gallic acid in food using an ultra-sensitive electrochemical sensor based on glass carbon electrode modified by bimetal doped carbon nanopolyhedras. Food Chemistry, 2023, 429: 136900,

[[26]] Badea M, di Modugno F, Floroian L, Tit D M, Restani P, Bungau S, et al.. Electrochemical strategies for gallic acid detection: potential for application in clinical, food or environmental analyses. Science of the Total Environment, 2019, 672: 129-140,

[[27]] Terbouche A, Boulahia S, Mecerli S, Ait-Ramdane-Terbouche C, Belkhalfa H, Guerniche D, et al.. A novel hybrid carbon materials-modified electrochemical sensor used for detection of gallic acid. Measurement, 2022, 187: 110369,

[[28]] Bart G, Fischer D, Samoylenko A, Zhyvolozhnyi A, Stehantsev P, Miinalainen I, et al.. Characterization of nucleic acids from extracellular vesicle-enriched human sweat. BMC Genomics, 2021, 22(1): 425,

[[29]] Kahkeshani N, Farzaei F, Fotouhi M, Alavi S S, Bahramsoltani R, Naseri R, et al.. Pharmacological effects of gallic acid in health and diseases: a mechanistic review. Iranian Journal of Basic Medical Sciences, 2019, 22(3): 225-237

[[30]] Serag A, Shakkour Z, Halboup A M, Kobeissy F, Farag M A. Sweat metabolome and proteome: recent trends in analytical advances and potential biological functions. Journal of Proteomics, 2021, 246: 104310,

[[31]] Montain S J, Cheuvront S N, Lukaski H C. Sweat mineral-element responses during 7 h of exercise-heat stress. International Journal of Sport Nutrition and Exercise Metabolism, 2007, 17(6): 574-582,

[[32]] Caballero B, Finglas P M, Toldrà F. . Encyclopedia of Food and Health, 2016 Salt Lake City Academic Press 268-272

[[33]] Liu F, Wang Y, Corke H, Zhu H. Dynamic changes in flavonoids content during congou black tea processing. LWT, 2022, 170: 114073,

[[34]] Shevchuk A, Megías-Pérez R, Zemedie Y, Kuhnert N. Evaluation of carbohydrates and quality parameters in six types of commercial teas by targeted statistical analysis. Food Research International, 2020, 133: 109122,

[[35]] Huber W, Koella J C. A comparison of three methods of estimating EC₅₀ in studies of drug resistance of malaria parasites. Acta Tropica, 1993, 55: 257-261,