Ultraversatile Fluorescent Sensors Based on Two Co^II/Ni^II Coordination Polymers for Identifying Various Antibiotics via the Turn-On/Off Effect and Detecting pH

Abstract

Because the accurate and rapid detection of antibiotics and pH plays an important role in biological systems and environmental fields, developing suitable and efficient sensors that can simultaneously detect antibiotics and pH has become important. In this work, we successfully designed and synthesized two new one-dimensional coordination polymers based on the mixed ligands L [N,N′-bis(4-methylpyridin-4-yl)-2,6-naphthalene dicarboxylamide] and Hfor CP 1, and M = Ni for CP 2), which were structurally characterized by single-crystal X-ray diffraction, infrared spectroscopy, powder X-ray diffraction, and thermogravimetric analysis. CP 1 and CP 2 can be used as ultraversatile fluorescent sensors, which can sense erythromycin (ERY) and oxacillin (OXC) by turn-on fluorescent enhancement and detect furaltadone (FTD) via the turn-off fluorescent quenching effect, separately. The concentration ranges of different analytes sensed by CPs 1 and 2 were 0−0.046 and 0−0.069 mM for ERY, 0−0.04 and 0−0.028 mM for OXC, and 0−0.155 and 0−0.019 mM for FTD, respectively. Moreover, CP 2 can effectively sense pH, in both a wide pH range and the fine physiological range. The sensors have a rapid luminescence response, good recyclability, and excellent fluorescence stability. More importantly, they not only represent the first example of detecting ERY or OXC based on fluorescent CPs but also are the very rare ultraversatile fluorescent sensors. The fluorescent sensing mechanism for antibiotics and pH was discussed in detail.

Metal–Organic Framework-Based Fluorescent Sensors for the Detection of Pharmaceutically Active Compounds

“…To illustrate, Yang et al integrated a Zn­(II)–organic framework (HNU-52) using the hydrothermal method, which was utilized for the detection of nitrofuran antibiotics based on the FRET mechanism . Another highly sensitive MOF-based sensor of furaltadone was reported by Wang et al, where the quenching mechanism was also explained with the help of FRET mechanism . Recently, some biomolecule sensors have been also reported where FRET was responsible for selective sensing. , In some literature, the selective sensing of Fe 3+ and several nitro explosives was also explained by FRET theory …”

A dual‐responsive luminescent sensor for efficient detection of 3‐nitrotyrosine and dipicolinic acid biomarkers based on copper(II) organic framework

“…By comparing the changes in the PXRD patterns of the recycled MOF samples with the initial ones (Figure S15), structural collapse can be first excluded 58,59 . Considering CuMOF displayed distinct response toward 3‐NT and DPA biomarkers, then the luminescence sensing mechanisms were studied by underlying photo‐induced electron transfer (PET) 1,60–64 . The LUMO and HOMO energy levels for free H 6 TPTA, 3‐NT, and DPA were calculated by using TD‐DFT with the help of Gaussian 09 software on a basis set of 6‐31G (d,p) for C H N O.…”

Two-Dimensional Lanthanide Metal–Organic Frameworks as a Platform for Sensing Pollutant and Nitrophenols Reduction

“…Among the fluorescent sensing materials, porous luminescent MOFs (LMOFs) is one of prevalent and efficient material and they have been used for fluorescence sensing applications because of their superior fluorescence properties. , The lanthanide-based MOFs (Ln-MOFs) have an excellent sensing performance during the detection process, and thereby, they have become unique luminescence materials for the significant application in the detection of water pollutant. − Herein, LCUH-105 exhibits an excellent fluorescence behavior due to its high selectivity and sensitivity for the detection of NFX, especially its fluorescence response mode is fluorescence enhancement (turn-on) during the detection process. As we well known, most of MOFs indicated fluorescence quenching mode during the process of detecting antibiotics, − while few fluorescence enhancement examples are used to detect antibiotics. − All the nitrogen atoms of TZI 3– in LCUH-105 did not participate in the coordination with metal ions; meanwhile, the tetrazole group has one negative charge, which made it to easily form hydrogen bonds with antibiotics. Therefore, the characteristic of ligand TZI 3– in LCUH-105 make the fluorescence resonance energy transfer easy to complete from antibiotics to ligand, resulting in the fluorescence enhancement (turn on) behavior toward norfloxacin (NFX).…”