Advances in Ultra-small Fluorescence Nanoprobes for Detection of Metal Ions, Drugs, Pesticides and Biomarkers.

Identification of trace level chemical species (drugs, pesticides, metal ions and biomarkers) plays key role in environmental monitoring. Recently, fluorescence assay has shown significant advances in detecting of trace level drugs, pesticides, metal ions and biomarkers in real samples. Ultra-small nanostructure materials (metal nanoclusters (NCs), quantum dots (QDs) and carbon dots (CDs)) have been integrated with fluorescence spectrometer for sensitive and selective analysis of trace level target analytes in various samples including environmental and biological samples. This review summarizes the properties of metal NCs and ligand chemistry for the fabrication of metal NCs. We also briefly summarized the synthetic routes for the preparation of QDs and CDs. Advances of ultra-small fluorescent nanosensors (NCs, QDs and CDs) for sensing of metal ions, drugs, pesticides and biomarkers in various sample matrices are briefly discussed. Additionally, we discuss the recent challenges and future perspectives of ultra-small materials as fluorescent sensors for assaying of wide variety of target analytes in real samples.

Simple hydrothermal approach for synthesis of fluorescent molybdenum disulfide quantum dots: Sensing of Cr3+ ion and cellular imaging.

Nowadays, fluorescent molybdenum disulfide quantum dots (MoS2 QDs) have proven to be potential candidates in the sensing and bioimaging areas owing to their exceptional intrinsic characteristics. Here, a simple hydrothermal strategy was explored for the preparation of MoS2 QDs using ammonium heptamolybdate and 6-mercaptopurine (6-MP) as precursors. The emission peak of MoS2 QDs was significantly quenched in the presence Cr3+ ion due to the selective surface chemistry on the surfaces of MoS2 QDs. The designed fluorescent MoS2 QDs showed a linear fluorescence quenching response with increasing concentration of Cr3+ ion (0.1-10 µM), allowing to detect Cr3+ ion even at 0.08 µM. This fluorescent MoS2 QDs were utilized for the quantification of Cr3+ ion in real samples (water and biological samples). Interestingly, the synthesized MoS2 QDs exhibited negligible cytotoxicity on NRK cells and acted as good candidates for imaging of Trichoderma viride fungal cells.

Acid Oxidation of Muskmelon Fruit for the Fabrication of Carbon Dots with Specific Emission Colors for Recognition of Hg2+ Ions and Cell Imaging.

In this study, water-soluble emissive carbon dots (CDs) are effectively fabricated with specific optical properties and colors by acid oxidation of muskmelon (Cucumis melo) fruit, which are termed as C. melo CDs (CMCDs). The fluorescence properties of CMCDs were tuned by controlling the experimental conditions that allow them to emit different colors, that is, blue (B-), green (G-), and yellow (Y-) CMCDs, with different emission wavelengths at 432, 515, and 554 nm when excited at 342, 415, and 425 nm, respectively. The fabricated multicolor-emissive CDs were confirmed by various analytical techniques. The sizes of B-, G-, and Y-CMCDs were found to be ∼3.5, ∼4.3, and ∼5.8 nm, respectively. The as-prepared CMCDs display stable emissions with quantum yields of 7.07, 26.9, and 14.3% for the three CMCDs, which could act as a promising probe for the selective detection of Hg2+ ions. Upon the addition of Hg2+ ions, the fluorescence intensity of G-CMCDs at 515 nm was quenched largely than that of B- and Y-CMCDs. The spectroscopic results display that the G-CMCDs acted as a sensor for the detection of Hg2+ ions with a wide linear range from 1.0 to 25 µM (R 2 = 0.9855) with a detection limit of 0.33 µM. This method was successfully applied to detect Hg2+ ions in biological and water samples. The fabricated multicolor-emissive CMCDs possess the cell (Cunninghamella elegans, Aspergillus flavus, and Rhizoctonia solani) imaging property, suggesting the biocompatible nature for multicolor imaging of various cells.

Influence of doping ion, capping agent and pH on the fluorescence properties of zinc sulfide quantum dots: Sensing of Cu2+ and Hg2+ ions and their biocompatibility with cancer and fungal cells.

Herein, a facile one-pot synthetic method was explored for the fabrication of glutathione capped Mn2+ doped­zinc sulphide quantum dots (GSH-Mn2+-ZnS QDs) for both fluorescent detection of Cu2+ and Hg2+ ions and for fluorescence imaging of two cancer (RIN5F and MDAMB231) and fungal (Rhizopus oryzae) cells. Particularly, doping of Mn2+ into ZnS QDs nanocrystal structure resulted a great improvement in the fluorescence properties of ZnS QDs. The emission peak of undoped ZnS QDs was found at 447 nm, which is due to the large number of surface defects in the ZnS QDs nanostructures. Under identical conditions, there is a good linear relationship between the quenching of fluorescence intensity and analytes (Cu2+ and Hg2+ ions) concentration in the range of 0.005 to 0.2 mM and of 0.025 to 0.4 mM for Cu2+ and Hg2+ ions, respectively. The GSH-Mn2+-ZnS QDs exhibit least cytotoxicity against RIN5F and MDAMB231 cells, demonstrating the multifunctional applications in sensing of metal ions and biocompatibility towards cancer (RIN5F and MDAMB231) and fungal (Rhizopus oryzae) cells.

Probing the selective separation of potassium ion from sodium ion with cyclopentadienyl anion as receptor: a computational study.

A systematic computational study has been carried out using post-Hartree-Fock and density functional theory methods on half sandwich (M-Cp), sandwich (Cp-M-Cp), inversed sandwich (M-Cp-M), and multi-decker chain complexes of alkali metal ions (Na(+), and K(+)). The binding affinity of cyclopentadienyl anion (Cp) with K(+) and Na(+) ions has been studied in half sandwich, sandwich, inversed sandwich, and multi-decker chain complexes. These complexes have been examined in the aqueous phase. The calculated results show that Cp anion can preferentially bind with Na(+) ion over K(+) ion in aqueous phase. The results obtained from DFT calculations have been compared with the crystal structures of Cp-Na and Cp-K complexes. The Bader's atoms in molecule (AIM) analysis were performed to characterize the non-covalent cation-π interactions in the Cp-M complexes. The calculated electron density at cage critical point indicates the strength of the Cp-M complexes. Energy decomposition analysis (EDA) has also been performed to investigate the origins of these interactions. The electrostatic interaction contributes significantly to the total interaction energy in Cp-M complexes. The relative stability difference of cyclopentadienyl anion (Cp) with K(+) and Na(+) ions in aqueous phase can be exploited for the separations from mixture such as sea bittern. The lower stability of K-Cp complex can induce to precipitate the K(+) ions more easily than the corresponding Na(+) ions. Graphical Abstract Potassium ion from sodium ion with cyclopentadienyl anion as receptor.