{"title":"将荧光染料加载到MOF孔中用于重金属离子的光学传感和吸附:合成、表征和性能","authors":"Xiaoqiang Pu , Juan Zhao","doi":"10.1016/j.saa.2025.126323","DOIUrl":null,"url":null,"abstract":"<div><div>The detection and removal of Cu(II) cations are an important topic in environmental protection and human health. Optical sensing platforms based on luminescent probes seem attractive due to their optical signal outputs which are free of electromagnetic interference, low cost, fast response, and high sensitivity. In this work, two azobenzene-based sensing probes (P1 and P2) were synthesized, and their sensing performance was firstly evaluated by their spectroscopic response towards various ions. P1 showed good sensing selectivity towards Cu<sup>2+</sup> by forming an adduct with stoichiometric ratio of 1:1, as confirmed by Job’s plot, NMR, XPS, and EPR (electron paramagnetic resonance) comparison. P2 showed sensing behavior not only towards Cu<sup>2+</sup> but also towards Fe<sup>2+</sup>, Fe<sup>3+</sup>, and Hg<sup>2+</sup> due to the increased bonding affinity of –OH group. These two azobenzene-based probes were then covalently loaded into a MOF (metal–organic framework) matrix of bio-MOF-1 to endow it with optical sensing ability, as well as to improve the adsorption stability/capacity for metal cations. P<sub>n</sub>@BMOF (n = 1, 2) samples were characterized by SEM, XRD, N<sub>2</sub> adsorption/desorption, IR, and elemental analysis. Their optical sensing and adsorption performance for metal cations were evaluated as well. Linear working equations were obtained with quenching constants and LOD values of 0.0884 μM<sup>−1</sup> and 0.22 μM for P1@BMOF, and 0.0998 μM<sup>−1</sup> and 0.20 μM for P2@BMOF. The adsorption levels for Cu<sup>2+</sup> were determined as 0.97 mmol/g for P1@BMOF and 1.03 mmol/g for P2@BMOF.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"340 ","pages":"Article 126323"},"PeriodicalIF":4.3000,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Loading fluorescent dyes into MOF pores for the optical sensing and adsorption of heavy metal ions: synthesis, characterization, and performance\",\"authors\":\"Xiaoqiang Pu , Juan Zhao\",\"doi\":\"10.1016/j.saa.2025.126323\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The detection and removal of Cu(II) cations are an important topic in environmental protection and human health. Optical sensing platforms based on luminescent probes seem attractive due to their optical signal outputs which are free of electromagnetic interference, low cost, fast response, and high sensitivity. In this work, two azobenzene-based sensing probes (P1 and P2) were synthesized, and their sensing performance was firstly evaluated by their spectroscopic response towards various ions. P1 showed good sensing selectivity towards Cu<sup>2+</sup> by forming an adduct with stoichiometric ratio of 1:1, as confirmed by Job’s plot, NMR, XPS, and EPR (electron paramagnetic resonance) comparison. P2 showed sensing behavior not only towards Cu<sup>2+</sup> but also towards Fe<sup>2+</sup>, Fe<sup>3+</sup>, and Hg<sup>2+</sup> due to the increased bonding affinity of –OH group. These two azobenzene-based probes were then covalently loaded into a MOF (metal–organic framework) matrix of bio-MOF-1 to endow it with optical sensing ability, as well as to improve the adsorption stability/capacity for metal cations. P<sub>n</sub>@BMOF (n = 1, 2) samples were characterized by SEM, XRD, N<sub>2</sub> adsorption/desorption, IR, and elemental analysis. Their optical sensing and adsorption performance for metal cations were evaluated as well. Linear working equations were obtained with quenching constants and LOD values of 0.0884 μM<sup>−1</sup> and 0.22 μM for P1@BMOF, and 0.0998 μM<sup>−1</sup> and 0.20 μM for P2@BMOF. The adsorption levels for Cu<sup>2+</sup> were determined as 0.97 mmol/g for P1@BMOF and 1.03 mmol/g for P2@BMOF.</div></div>\",\"PeriodicalId\":433,\"journal\":{\"name\":\"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy\",\"volume\":\"340 \",\"pages\":\"Article 126323\"},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2025-05-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1386142525006298\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"SPECTROSCOPY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1386142525006298","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"SPECTROSCOPY","Score":null,"Total":0}
Loading fluorescent dyes into MOF pores for the optical sensing and adsorption of heavy metal ions: synthesis, characterization, and performance
The detection and removal of Cu(II) cations are an important topic in environmental protection and human health. Optical sensing platforms based on luminescent probes seem attractive due to their optical signal outputs which are free of electromagnetic interference, low cost, fast response, and high sensitivity. In this work, two azobenzene-based sensing probes (P1 and P2) were synthesized, and their sensing performance was firstly evaluated by their spectroscopic response towards various ions. P1 showed good sensing selectivity towards Cu2+ by forming an adduct with stoichiometric ratio of 1:1, as confirmed by Job’s plot, NMR, XPS, and EPR (electron paramagnetic resonance) comparison. P2 showed sensing behavior not only towards Cu2+ but also towards Fe2+, Fe3+, and Hg2+ due to the increased bonding affinity of –OH group. These two azobenzene-based probes were then covalently loaded into a MOF (metal–organic framework) matrix of bio-MOF-1 to endow it with optical sensing ability, as well as to improve the adsorption stability/capacity for metal cations. Pn@BMOF (n = 1, 2) samples were characterized by SEM, XRD, N2 adsorption/desorption, IR, and elemental analysis. Their optical sensing and adsorption performance for metal cations were evaluated as well. Linear working equations were obtained with quenching constants and LOD values of 0.0884 μM−1 and 0.22 μM for P1@BMOF, and 0.0998 μM−1 and 0.20 μM for P2@BMOF. The adsorption levels for Cu2+ were determined as 0.97 mmol/g for P1@BMOF and 1.03 mmol/g for P2@BMOF.
期刊介绍:
Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy (SAA) is an interdisciplinary journal which spans from basic to applied aspects of optical spectroscopy in chemistry, medicine, biology, and materials science.
The journal publishes original scientific papers that feature high-quality spectroscopic data and analysis. From the broad range of optical spectroscopies, the emphasis is on electronic, vibrational or rotational spectra of molecules, rather than on spectroscopy based on magnetic moments.
Criteria for publication in SAA are novelty, uniqueness, and outstanding quality. Routine applications of spectroscopic techniques and computational methods are not appropriate.
Topics of particular interest of Spectrochimica Acta Part A include, but are not limited to:
Spectroscopy and dynamics of bioanalytical, biomedical, environmental, and atmospheric sciences,
Novel experimental techniques or instrumentation for molecular spectroscopy,
Novel theoretical and computational methods,
Novel applications in photochemistry and photobiology,
Novel interpretational approaches as well as advances in data analysis based on electronic or vibrational spectroscopy.