Multiple Interpenetrating Metal–Organic Frameworks with Channel-Size-Dependent Behavior for Selective Gossypol Detection and Perovskite Quantum Dot Encapsulation

Abstract

An interpenetrating structure endows metal–organic frameworks (MOFs) with many exciting applications, such as fluorescence detection and host–guest chemistry. Herein, two unique structure-interpenetrating In-MOFs (In-pdda-1 and In-pdda-2; H2pdda = 4,4′-(pyridine-2,5-diyl)dibenzoic acid) are constructed by different coordination configurations. The four-connected In3+ center shows a triangular-pyramidal configuration or a 2D rectangle, forming an unc topology for In-pdda-1 and a sql network for In-pdda-2, respectively. Two different interpenetrating modes created by linear rigid ligands and metal clusters are observed in the two MOFs (In-pdda-1, 8-fold interpenetrating mode; In-pdda-2, [2D + 2D] interpenetrating mode), which determine the channel-size-dependent properties in fluorescence applications. During the quantitative detection process of gossypol, the small rhombic channels divided by interpenetrating molecular planes of In-pdda-2 greatly limit the distance between the analyte and the probe, promoting electron transfer and energy transfer processes and thus resulting in a low detection limit (28.6 nM). In addition, the pore size effect of In-pdda-1 encouraged us to explore an in situ perovskite quantum dot encapsulation strategy to obtain a MAPbBr3@MOF material with tunable and stable luminescence properties. Both of the above channel-size-dependent fluorescence properties may provide inspiration for the structural design and specialized applications of MOF materials.

Ratiometric Fluorescence Thermometry, Quantitative Gossypol Detection, and CO2 Chemical Fixation by a Multipurpose Europium (III) Metal–Organic Framework

“…It is well known that accurate temperature is a crucial physical parameter for humans and plays a significant role in daily life, industrial production, scientific research, etc. , One such appealing temperature measurement method is the noncontact optical temperature sensing strategy based on Ln-MOFs, which can be utilized in some extreme conditions such as strong electromagnetic fields, fast-evolving objects, microstructures, and high voltage and can overcome the defects of traditional contact temperature measurement method through the variations of luminescence of the Ln-MOFs. − Thus, the noncontact optical temperature sensing strategy based on Ln-MOFs has attracted extensive research interest thanks to its fast response, high sensitivity, safe operation, and the possibility of remote or noninvasive monitoring. , In particular, ratiometric thermometry based on the dual luminescent intensity ratio of the Ln-MOFs can endow the noncontact measurement with self-calibrated ability, thus avoiding disturbance from background light and showing a broad application prospect. , However, these Ln-MOFs involving single-lanthanide luminescent centers as ratiometric luminescence sensors lack attention. In addition, as a natural polyphenolic toxin concentrated in cottonseeds, gossypol is widely observed in cottonseed products such as crude cottonseed oil, which is confirmed to have great risks to the safe consumption in the food industry. − The excess of gossypol beyond the normal range would accumulate toxins and severely cause several adverse human health problems such as hepatoxicity, neurological disorders, and immunotoxicity. − The maximum concentration of free gossypol in edible cottonseed oil has been defined as low as 200 ppm by the Chinese Ministry of Health and is permitted in various animal feed materials, and complete feeding stuffs range from 20 to 5000 ppm by the European Union. , Therefore, the gossypol must be removed from the cottonseed products to ensure the concentration of gossypol at a safe standard and it is of significant necessity to investigate a sensitive and facile approach for gossypol detection, of which luminescent Ln-MOFs are considered as optimized candidates. Apart from exploiting photoluminescence sensing performance, Ln-MOFs offer interesting heterogeneous catalysis for the conversion of CO 2 into cyclic carbonates. − As an inexpensive, nontoxic, and the most abundant C1 resource, the conversion of CO 2 into valuable cyclic carbonates catalyzed by Ln-MOFs is one of the most promising strategies, owing to its 100% atomic economy during the reaction process.…”

Highly Luminescent Lanthanide Metal‐Organic Frameworks with Tunable Color for Nanomolar Detection of Iron(III), Ofloxacin and Gossypol and Anti‐counterfeiting Applications

“…Taking into account the fast response of NIIC‐1‐Tb towards Fe 3+ and OFX, its sensing performance for gossypol was evaluated. The sensing experiments were carried out following the route described above for OFX (Figure 3g) and a linear luminescence quenching response was observed in the concentration range of gossypol 10–80 nM (Figure 3h) with K sv value of 9.09×10 6 M −1 and LOD of 2.27 nM, which is second only to Tb‐MOF mentioned above and surpasses other MOF sensors (Table S7) [40–45] . Of particular interest is that NIIC‐1‐Tb demonstrates a much faster response of less than 100 s (Figure 3i) and in this parameter it surpasses the most sensitive MOFs (Table S7).…”

“…The sensing experiments were carried out following the route described above for OFX (Figure 3g) and a linear luminescence quenching response was observed in the concentration range of gossypol 10-80 nM (Figure 3h) with K sv value of 9.09 × 10 6 M À 1 and LOD of 2.27 nM, which is second only to Tb-MOF mentioned above and surpasses other MOF sensors (Table S7). [40][41][42][43][44][45] Of particular interest is that NIIC-1-Tb demonstrates a much faster response of less than 100 s (Figure 3i) and in this parameter it surpasses the most sensitive MOFs (Table S7). In addition, the absence of notable interference from blood plasma and urine components for gossypol determination was confirmed (Figure S25).…”

Highly Luminescent Lanthanide Metal‐Organic Frameworks with Tunable Color for Nanomolar Detection of Iron(III), Ofloxacin and Gossypol and Anti‐counterfeiting Applications

“…The sensing experiments were carried out following the route described above for OFX (Figure 3g) and a linear luminescence quenching response was observed in the concentration range of gossypol 10-80 nM (Figure 3h) with K sv value of 9.09 × 10 6 M À 1 and LOD of 2.27 nM, which is second only to Tb-MOF mentioned above and surpasses other MOF sensors (Table S7). [40][41][42][43][44][45] Of particular interest is that NIIC-1-Tb demonstrates a much faster response of less than 100 s (Figure 3i) and in this parameter it surpasses the…”