Fluorescent Carbon Dots: Aggregation-Induced Emission Enhancement, Application as Probe for CN- and Cr2O7-2, Sensing Strips and Bio-imaging Agent.

Fluorescent carbon dots (Trp-CDs) were prepared using tryptophan as precursor and were characterized on the basis of elemental analysis, powder-XRD, IR, Raman spectroscopy, 13C-NMR, UV-Vis, fluorescence and TEM. Trp-CDs exhibit poor fluorescence in 100% water but showed strong Aggregation Induced Emission (AIE) in ethanol and higher alcohols. The anion sensing study of Trp-CD revealed that it selectively detects CN- and Cr2O7-2 and from fluorescence quenching titration study, quenching constant, LOD and range of detection were evaluated. The emission life-time of Trp-CD before and after addition of CN- and Cr2O7-2 were measured, the decay curve before addition of anion was best fitted with a bi-exponential function with life-time of τ1 2.79 ns (10.74%) and τ2 18.93 ns (89.26%). The mechanistic study revealed that for CN-, the fluorescence quenching is due to its interaction with protons attached to surface functional groups and for Cr2O7-2, it is due to inner filter effect (IFE). Sensing strips were prepared by coating Trp-CDs onto various solid surfaces including agarose films and were used for detection of CN- and Cr2O7-. Trp-CD was found to be nontoxic and biocompatible and used as staining agent for Artemia and Bacteria (Bacillus Subtilis, Pseudomonas) and detection of CN- and Cr2O7-.

Rosmarinic Acid-Capped Silver Nanoparticles for Colorimetric Detection of CN- and Redox-Modulated Surface Reaction-Aided Detection of Cr(VI) in Water.

Rosmarinic acid-capped silver nanoparticles (Ro-AgNPs) were prepared and applied as a probe for selective colorimetric detection of cyanide (CN-) and chromium(VI) [Cr(VI)] under different conditions in aqueous media. The carbon atom of CN- interacts with the AgNPs, and the carbon atom donates electrons from the HOMO to the vacant orbitals of the coordinatively unsaturated surface atom (Ag0). After donating electrons, CN- attached onto the surface of the nanoparticles becomes very reactive and interacts with dissolved oxygen and generates reactive oxygen species (ROS) such as superoxide (O2 -), singlet oxygen (1O2), and so forth. In this process, Ag0 oxidizes to Ag+ and combines with CN- forming water-insoluble AgCN, and the ROS (O2 -) formed reacts with Ag/Ag+ to form Ag2O. The oxidation of Ag0 to Ag+ resulted in dissolution of AgNPs, which causes disappearance of the surface plasmon resonance band and color change from yellow to colorless. For detection of Cr(VI), ascorbic acid and CN- were added first; the ascorbic acid replaced the rosmarinic acid and then reduced the added Cr(VI) to Cr(III), and, in this process, ascorbic acid was oxidized to dehydroascorbic acid, which moved away from the nanoparticles' surface. CN- then interacted with the surface Ag0 atom, got activated, and interacted with dissolved oxygen forming Ag+ and ROS, which then followed the same process as described for CN- to form AgCN and Ag2O with a color change. The limits of detection were found to be 0.01 and 0.03 µM for CN- and Cr(VI), respectively. The material was also used for sensing CN- and Cr(VI) in real samples, and the results obtained were satisfactory. For field application, agarose-based strips were prepared by immobilizing the nanoparticles onto the agarose film and successfully used for the detection of CN- and Cr(VI) in water.

Microwave-assisted synthesis of nitrogen-doped carbon dots using prickly pear as the carbon source and its application as a highly selective sensor for Cr(VI) and as a patterning agent.

Preparation of water-dispersible carbon dots from inexpensive natural carbon precursors and its application for purposes such as sensing, bio-imaging and patterning agents is showing growing interest in recent years. In this study, we have reported the preparation of nitrogen-doped carbon dots (N-CDs) using prickly pear as the carbon source and m-xylylenediamine as the nitrogen source using a one-step microwave-assisted synthetic process. The N-CDs prepared were characterized on the basis of elemental analysis, XPS, powder-XRD, FT-IR, Raman, TEM, UV-vis and fluorescence spectroscopy. Doping of nitrogen in the N-CDs made them highly fluorescent and the study on their ion-recognition property revealed that they detect highly toxic Cr(VI) with high selectivity and sensitivity (LOD, 0.04 µM) and without interference from the other ions used in this study. By immobilizing these N-CDs onto filter paper, sensor strips were prepared for on-site monitoring/field applications and they were successfully used for the detection of Cr(VI) in water. Detailed spectral analysis revealed that the mechanism of Cr(VI) sensing involved a phenomenon called the "inner filter effect" and analysis of the fluorescence lifetime data suggested the "static quenching" of fluorescence intensity. These N-CDs were used to prepare fluorescent carbon ink and were successfully used as patterning agents.

A New Molecular Probe for Colorimetric and Fluorometric Detection and Removal of Hg2+ and its Application as Agarose Film-Based Sensor for On-Site Monitoring.

A new molecule incorporating two units of 7-nitro-benzoxadiazole (NBD), bridged by m-xylylenediamine, was synthesized and characterized on the basis of analytical and spectroscopic techniques. The metal ion sensing property of this molecule was studied spectroscopically with a large number of metal ions. This study revealed that it can perform as a dual-channel probe for colorimetric as well as fluorometric detection of Hg2+. In presence of Hg2+, a substantial change in UV-Vis spectrum with the appearance of a new band at 545 nm and a distinct colour change from yellow to red was observed. In the fluorescence spectrum, the intensity of the emission band was substantially quenched only upon addition of Hg2+. No significant interference from any other metal ion used in this study was noted, the limit of detection (LOD) for Hg2+ was found to be 60 and 10 nM for colorimetric and fluorometric detection method, respectively. This new chemosensor was used for removal of Hg2+ from aqueous solution with 92% efficiency. For on-site monitoring and field application, this molecule was immobilized into the agarose based hydrogel film, which was used successfully for detection of Hg2+ in water. The study on reversible behaviour of this chemosensor revealed that it can be recycled in solution as well as in solid phase by treatment with Na2S.

Colorimetric dual sensor for Cu(II) and tyrosine and its application as paper strips for detection in water and human saliva as real samples.

A calix[4]arene based compound incorporating amide and morpholine moieties has been synthesized and its ion recognition property towards metal ions and application of its metal complex towards sensing of amino acids has been investigated. The synthesized compound interacts with Cu2+ with high selectivity and sensitivity (LOD, 0.1 ppb) in aqueous media with instant color change from colorless to yellow without interference from any other metal ions used in this study. The molecular structure of the calix compound (1) has been determined by single crystal X-ray study and the structure of its Cu2+ complex has been established by DFT calculation. The Cu2+ complex of 1 selectively detects tyrosine (LOD, 1.2 ppm) in water with distinct color change and without any interference from other 22 amino acids used in this study. The mechanism for detection of tyrosine with color change is also presented. For easy field application, paper based sensor strips have been prepared by coating compound 1 and its Cu2+ complex on filter paper, which have been used for semi-quantitative measurement of Cu2+ and tyrosine. Compound 1 and its Cu2+ complex have also been used for detection of Cu2+ and tyrosine, respectively in water and human saliva as real samples and satisfactory results are obtained.

Synthesis of Calixarene-Capped Silver Nanoparticles for Colorimetric and Amperometric Detection of Mercury (HgII, Hg0).

Calixarene-functionalized water dispersible silver nanoparticles have been synthesized and characterized on the basis of UV-vis, IR, X-ray diffraction, and high-resolution transmission electron microscopy analysis, and their sensing properties toward metal ions have been investigated. They selectively detect Hg2+ and Hg0 in solution and vapor phases, respectively, with distinct color change. Interference study with mixture of metal ions revealed no interference from any other metal ions used in this study. Their mechanism of detection involved Hg2+-aided displacement of calixarene moiety from the surface of the functionalized nanoparticles, followed by the formation of Ag-Hg amalgam due to interaction of Hg2+ with Ag0 and also the formation of assembly of Ag0 nanoparticles by dipole-dipole interaction of the bare-surfaced nanoparticles. Electrochemical study revealed that with the aid of functionalized nanoparticles, Hg2+ can be detected amperometrically with high sensitivity. The detection limits obtained for Hg2+ by UV-vis study and amperometry are 0.5 nM (0.1 ppb) and 10 nM (2 ppb), respectively. The new material has been used to detect Hg2+ in aqueous real sample and Hg0 in soil sample.

Tinospora cordifolia derived biomass functionalized ZnO particles for effective removal of lead(ii), iron(iii), phosphate and arsenic(iii) from water.

Owing to the vast diversity in functional groups and cost effectiveness, biomass can be used for various applications. In the present study, biomass from Tinospora cordifolia (TnC) was prepared and grafted onto the surface of ZnO particles following a simple method. The TnC functionalized ZnO particles (ZnO@TnC) were characterized and exhibited excellent adsorption properties towards Pb2+ (506 mg g-1), Fe3+ (358 mg g-1) and PO4 3- (1606 mg g-1) and the Fe3+ adsorbed ZnO@TnC adsorbs AsO2 1- (189 mg g-1); the metal ions and anions were analyzed by ICP and IC. For reuse of ZnO@TnC, a desorption study was successfully carried out using NaOH and EDTA for PO4 3- and Pb2+, respectively; Fe3+ was further used for adsorption of As(iii). The adsorption fits well with the Langmuir adsorption isotherm model and the adsorption kinetic data are best fitted with a pseudo-second-order equation. The system developed may be useful for treatment of waste water and industrial effluents.

Green route for synthesis of multifunctional fluorescent carbon dots from Tulsi leaves and its application as Cr(VI) sensors, bio-imaging and patterning agents.

We report a one pot green strategy for the synthesis of carbon dots using tulsi leaves and their potential application in sensing of Cr(VI) selectively. The detection mechanism is based on the phenomenon called inner filter effect (IFE) and a good linear static quenching was observed in the range of 1.6 µM to 50 µM with a detection limit of 4.5 ppb. The reversible switching in fluorescence has been tested and a good recovery in fluorescence was observed up to three consecutive cycles upon addition of ascorbic acid as reducing agent. Also the low toxicity, high fluorescence and photostabilty of the CDs make them excellent imaging and patterning agent. The acid and alkali resistant property of these CDs makes it suitable for real sample analysis. The fluorescent CDs were applied for successful detection of Cr(VI) in water with spike-recoveries ranging from 93 to 99%.

New Route for Synthesis of Fluorescent SnO2 Nanoparticles for Selective Sensing of Fe(III) in Aqueous Media.

A simple new route for synthesis of fluorescent SnO2 and its application as an efficient sensing material for Fe3+ in aqueous media is reported. The fluorescent SnO2 nanoparticles were obtained by oxidation of SnCl2, which when used as reducing agent for the reduction of organic nitro compounds to corresponding amino compounds in ethanol. The SnO2 nanoparticles have been characterized on the basis of powder-XRD, IR, UV-Vis, TEM, FESEM and EDX analysis and found that this material is highly fluorescent in aqueous media. Detail study revealed that this material functions as a selective probe for Fe3+ out of a large number of metal ions used. The oxygen vacancies (defects) generated on the surface of the SnO2 during synthesis, are the source of emission due to recombination of electrons with the photo-excited hole in the valance bond. The quenching of emission intensity in presence of Fe3+ is due to the nonradiative recombination of electrons and holes at the surface. This material is used for estimation of Fe3+ in real samples such as drinking water, tap water and soil.

Sunlight Induced Preparation of Functionalized Gold Nanoparticles as Recyclable Colorimetric Dual Sensor for Aluminum and Fluoride in Water.

A sunlight induced simple green route has been developed for the synthesis of polyacrylate functionalized gold nanoparticles (PAA-AuNPs), in which poly(acrylic acid) functions as a reducing as well as stabilizing agent. This material has been characterized on the basis of spectroscopic and microscopic studies; it exhibited selective colorimetric detection of Al3+ in aqueous media, and the Al3+ induced aggregated PAA-AuNPs exhibited detection of F- with sharp color change and high selectivity and sensitivity out of a large number of metal ions and anions tested. The mechanistic study revealed that, for Al3+, the color change is due to a shift of the SPR band because of the Al3+ induced aggregation of PAA-AuNPs, whereas for F-, the reverse color change (blue to red) with return of the SPR band to its original position is due to dispersion of aggregated PAA-AuNPs, as F- removes Al3+ from the aggregated species by complex formation. Only concentration-dependent fluoride ion can prevent Al3+ from aggregating PAA-AuNPs. The method is successfully used for the detection of F- in water collected from various sources by the spiking method, in toothpastes of different brands by the direct method. The solid Al3+-PAA-AuNPs were isolated, adsorbed on ZIF@8 (zeolitic imidazolate framework) and on a cotton strip, and applied as solid sensing material for detection of F- in aqueous media.

Silver nanoparticle based highly selective and sensitive solvatochromatic sensor for colorimetric detection of 1,4-dioxane in aqueous media.

A citrate stabilised silver nanoparticle (Ci-AgNP) based solvatochromic sensor, which functions as a highly selective and sensitive colorimetric probe for 1,4-dioxane in aqueous media is reported. The surfaces of the AgNPs generate reactive oxygen species, which promote the degradation of 1,4-dioxane assembled in the vicinity of the nanoparticle surfaces through charge transfer interactions. During this process, Ag(0) is oxidised to Ag(+) and the yellow colour of the solution turns to colourless. The sensor was used for the estimation of 1,4-dioxane in ground water and also 1,4-dioxane vapour diffused in aqueous media.