ABSTRACT
Due to the severe toxicity of triethylamine (TEA), the preparation of chemsensors with high sensitivity, low cost and visualization for TEA detection has been a research hotspot. However, based on the fluorescence turn-on detection of TEA remains rare. In this work, three two-dimensional conjugated polymers (2D CPs) were prepared by chemical oxidation polymerization. These sensors show a quick response and excellent selectivity toward TEA at room temperature. The minimum limit of detection (LOD) for TEA was 3.6 nM in the range of 10 µM â¼ 30 µM. Interestingly, the paper sensor based on P2-HCl can quantitatively detect TEA gas within 20 s, which showed great application potential in fields of environmental monitoring. Besides, Fourier transform infrared spectra (FT-IR), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) data were used to thoroughly interpret the sensing mechanism. This work provided an effective method for the development of 2D fluorescent chemosensors for TEA detection.
ABSTRACT
It is important to achieve a moderate sustained release rate for drug delivery, so it is critical to regulate the host-guest interactions for the rational design of a carrier. In this work, a nano-sized biocompatible metal-organic framework (MOF), Mg(H2TBAPy)(H2O)3·C4H8O2 (TDL-Mg), was constructed by employing π-conjugated 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) as a ligand and used for 5-fluorouracil (5-FU) loading (28.2 wt %) and sustained slow release. TDL-Mg exhibits a 3D supramolecular architecture featuring a 1D rectangle channel with a size of 6.2 × 8.1 Å2 and a Brunauer-Emmett-Teller surface area of 627 m2·g-1. Channel microenvironment analysis shows that the rigid H2TBAPy2- ligand adopts special torsion to stabilize the channels and offer rich π-binding sites; the partially deprotonated carboxyls not only participate in the formation of strong hydrogen bonds but also create a mild pH buffer environment for biological applications. Suitable host-guest interactions are generated by the synergistic effect of polydirectional hydrogen bonds, multiple π-interactions, and confined channels, which allow 5-FU@TDL-Mg to release 76% of load in 72 h, a medically reasonable rate. Microcalorimetry was used to directly quantify these host-guest interactions with a moderate enthalpy of 22.3 kJ·mol-1, which provides a distinctive thermodynamic interpretation for understanding the relationship between the MOF design and the drug release rate. Additionally, the nano-sized 5-FU@TDL-Mg can be taken up by mouse breast cancer cells (4T1 cells) for imaging based on the dramatic fluorescence change during the release of 5-FU, exhibiting potential applications in biological systems.
