Design of silver nanoparticle-embedded nano zirconium-based metal-organic frameworks for highly sensitive detection of chlorpyrifos in real samples.

Chlorpyrifos (CPS) is widely found in food and water sources due to agricultural use, posing health and environmental risks. Therefore, this work introduces a fluorescent sensor design of silver nanoparticle-embedded nano zirconium-based metal-organic frameworks (UiO-66-NH2@AgNPs) for accurate examination of CPS. Briefly, UiO-66-NH2 was synthesized hydrothermally, exhibiting weak luminescence owed to ligand-to-metal charge transfer (LMCT). Here, it limits its direct utility in fluorescence-based detection. To address this limitation, silver nanoparticles (AgNPs) were introduced into UiO-66-NH2, enhancing fluorescence via the metal-enhanced fluorescence (MEF) effect. Briefly, a comprehensive spectral analysis such as XPS, SEM, TEM, PXRD, etc., was performed to validate the synthesis of UiO-66-NH2@AgNPs. Subsequent evaluation revealed that CPS effectively quenched the luminescence intensity of UiO-66-NH2@AgNPs through a static quenching mechanism. The fluorescence intensity exhibited good linearity with CPS concentration in the span of 10 to 1,000 ng/mL, with a recognition limit of 191.5 ng/mL(S/N = 3). The interaction involved Ag-S bond formation and electrostatic interactions, reducing fluorescence intensity. The method was confirmed through successful CPS detection in fruit samples. The UiO-66-NH2@AgNPs nanoprobe offers a simple, sensitive, and accurate platform for CPS sensing, with potential for future use in detecting CPS in fruits and vegetables.

Designed fluorescence "on-off-on" probe based on cobalt, zinc, and nitrogen co-doped graphene quantum dots: A case of quinalphos sensing.

In this study, we developed a new fluorescence "on-off-on" sensor utilizing water-soluble cobalt/zinc-nitrogen co-doped graphene quantum dots (Co/Zn-N-GQDs) to recognize quinalphos pesticide in vegetable and fruit samples. Primarily, the synthesis method employed a one-pot hydrothermal approach, using betel leaves as a natural precursor and cobalt ("Co"), zinc ("Zn"), and urea ("N") as dopant sources. The Co/Zn-N-GQDs probes underwent comprehensive analytical characterization. The Co/Zn-N-GQDs were synthesized with a remarkable luminescence yield of 31.49%, exhibiting excitation at 320 nm and emission peak at 393 nm. Interestingly, the luminescence of Co/Zn-N-GQDs was selectively "Turned Off" by Cu2+ via a static quenching setup. Remarkably, quenched fluorescence was surprisingly reactivated upon adding quinalphos to the quench setup, indicating a direct correlation between luminescence reactivation and quinalphos concentration. Briefly, this phenomenon is ascribed to the functional groups in quinalphos, such as quinoxalinyl and phosphorothioate, which chelate with Cu2+ ions, disrupting the nonfluorescent Cu2+-Co/Zn-N-GQDs complex. The design sensor demonstrated a limit of detection (LOD) of 0.11 µM and a broad linear span of 0.5 to 200 µM. In conclusion, Cu2+-Co/Zn-N-GQDs sensor showed immediate applicability, stability, and reproducibility, making it highly effective for quinalphos sensing in various samples.