A dual-response ratiometric fluorescent sensor by europium-doped silicon nanoparticles for fluorescent and smartphone imaging detection of tetracycline.

Given the threat to human health posed by the abuse of tetracycline (TC), the development of a portable, on-site methods for highly sensitive and rapid TC detection is crucial. In this work, we initially synthesized europium-doped silicon nanoparticles (SiEuNPs) through a facile one-pot microwave-assisted method. Due to its blue-red dual fluorescence emission (465 nm/621 nm), which was respectively attributed to the silicon nanoparticles and Eu3+, SiEuNPs were designed as a ratiometric fluorescent sensor for TC detection. For the dual-signal reverse response mechanism: TC quenched the blue emission from silicon nanoparticles through inner filter effect (IFE), and enhanced the red emission through "antenna effect" (AE) between TC and Eu3+, the nanoprobe was able to detect TC within a range of 0.2-10 µM with a limit of detection (LOD) of 10.7 nM. Notably, the equilibrium detection time was only 1 min, achieving rapid TC detection. Furthermore, TC was also measured in real samples (tap water, milk and honey) with recoveries ranging from 95.7 % to 117.0 %. More importantly, a portable smartphone-assisted on-site detection platform was developed, enabling real-time qualitative identification and semi-quantitative analysis of TC based on fluorescence color changes. This work not only provided a novel doped silicon nanoparticles strategy, but also constructed a ratiometric sensing platform with dual-signal reverse response for intuitive and real-time TC detection.

Dual-reverse-signal ratiometric fluorescence method for malachite green detection based on multi-mechanism synergistic effect.

The proposition of ratiometric detection mode has demonstrated great superiority in improving analysis accuracy by forming self-calibration. Herein, the novel dual-reverse-signal ratiometric fluorescence detection for malachite green (MG) was first achieved based on synergistic effect of fluorescence resonance energy transfer (FRET) and inner filter effect (IFE). The ratiometric fluorescence probe (B-RCDs) was self-assembled via electrostatic attraction between blue-emission carbon dots (BCDs) and red-emission carbon dots (RCDs), followed with FRET effect from BCDs to RCDs and exhibited dual-emission at 450 nm and 627 nm. In the presence of MG, the IFE effect between MG and RCDs quenched the fluorescence at 627 nm and restored the fluorescence at 450 nm, sending out two reverse signals along with an obvious color change from pink to purple (302 nm UV lamp). This ratiometric method not only simplified the preparation process, but also improved the detection sensitivity, showing a low limit of detection (LOD) of 41.8 nM, which exhibited superiority than that of single-signal RCDs (157.3 nM). This method held a rapid response of 10 min and represented satisfactory recoveries (99.14%-109.08%) in real water samples, revealing it was a promising candidate in the fast, sensitive and practical detection of MG. Moreover, the design of synergistic effect supplied a new perspective for the development of ratiometric sensing in the future.

Preparation of Dual-Template Epitope Imprinted Polymers for Targeted Fluorescence Imaging and Targeted Drug Delivery to Pancreatic Cancer BxPC-3 Cells.

Molecularly imprinted polymers were commonly used for drug delivery. However, single-template molecularly imprinted polymers often fail to achieve both drug delivery and precise targeting. To address this issue, a dual-template molecularly imprinted polymer nanoparticle used for targeted diagnosis and drug delivery for pancreatic cancer BxPC-3 cells (FH-MIPNPs) was prepared. In the FH-MIPNPs, the 71-80 peptide of human fibroblast growth-factor-inducible 14 modified with glucose (Glu-FH) and bleomycin (BLM) were used as templates simultaneously, so that the FH-MIPNPs could load BLM and bind to the BxPC-3 cells, which overexpress human fibroblast growth-factor-inducible 14 (FN14). Targeted imaging experiments in vitro show that the FH-MIPNPs could specifically target BxPC-3 cells and that there is no targeting effect on cells without expression of FN14. In vivo antitumor experiment results demonstrated that the FH-MIPNP-loaded BLM (FH-MIPNPs/BLM) could inhibit the growth of xenografts tumor of BxPC-3 (tumor volume increased to 1.05×), which shows that FH-MIPNPs/BLM had obvious targeted therapeutic effect compared to the other three control groups of BLM, FH-NIPNPs/BLM, and physiological saline (tumor volume increased to 1.5×, 1.6×, and 2.4×, respectively). What is more, FH-MIPNPs have low biotoxicity through toxicity experiments in vitro and in vivo, which is favorable toward making molecularly imprinted polymers an effective platform for tumor-targeted imaging and therapy.