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-.

Correction: Highly active spherical amorphous MoS2: facile synthesis and application in photocatalytic degradation of rose bengal dye and hydrogenation of nitroarenes.

[This corrects the article DOI: 10.1039/C5RA19442C.].

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%.

Solvent-free production of nano-FeS anchored graphene from Ulva fasciata: A scalable synthesis of super-adsorbent for lead, chromium and dyes.

Here we demonstrate, a simple and solvent-free synthetic route for the production of FeS/Fe(0) functionalized graphene nanocomposite (G-Fe) via a one-step pyrolysis of seaweed biomass (Ulva fasciata). It is proposed that the natural abundance of both inorganic and organic sulfur in the seaweed induces the reduction of exfoliated graphitic sheets at elevated temperatures. FeCl3 was employed both as the iron precursor as well as the templating agent. Iron doping played a dual-faceted role of exfoliating as well as activating agent, producing composite with high adsorption capacity for Pb2+ (645 ±â€¯10 mg/g), CR (970 mg/g), CV(909 mg/g), MO (664 mg/g), MB (402 mg/g) dyes and good recyclability (8 cycles). Pb2+ adsorption was irreversible even at low pH values and the spent composite (G-Fe-Pb) was utilized for efficient Cr(IV) removal (Ì´100 mg/g). The adsorption data followed the pseudo second order kinetics while the equilibrium data fitted perfectly into the Langmuir adsorption equation. Further, a thin layer of composite was deposited on a filter paper by vacuum filtration which was tested under continuous filtration mode for RB5 dye removal. Preliminary results highlight the potential of this composite to be used in pretreatment steps in hybrid membrane processes for filtration of complex wastewater feeds.

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.

Fenofibrate Nanocrystals Embedded in Oral Strip-Films for Bioavailability Enhancement.

The aim of the present study was to make a fenofibrate (FNB) nanocrystal (NC) by wet media milling, characterizations and formulates into oral strip-films (OSFs). Mechanical properties, redispersion study, and solid-state characterizations results suggested that reduction of drug crystal size at nanoscale and incorporation into OSFs does not affect the solid-state properties of the drug. In vitro dissolution kinetics showed enhanced dissolution rate was easily manipulated by changing the thickness of the OSF. In situ UV-imaging was used to monitor drug dissolution qualitatively and quantitatively in real time. Results confirm that the intrinsic dissolution rates and surface drug concentration measured with this device were in agreement with the USP-IV dissolution profiles. In vivo pharmacokinetics in rabbits showed a significant difference in the pharmacokinetics parameter (1.4 fold increase bioavailability) of FNB NC-loaded OSFs as compared to the marketed formulation "Tricor" and as-received (pristine) drug. This approach of drug nanocrystallization and incorporation into OSFs may have significant applications in cost-effective tools for bioavailability enhancement of FNB.

Fluorescent carbon nanoparticles obtained from charcoal via green methods and their application for sensing Fe3+ in an aqueous medium.

Two green methods (microwave and hydrothermal) were employed for the preparation of water dispersible fluorescent carbon nanoparticles (CNPs) from activated charcoal. Microwave and hydrothermally synthesized carbon nanoparticles, (MW-CNPs) and (HT-CNPs), respectively were characterized by microscopic and spectroscopic techniques. A detailed study of their fluorescence characteristics was made. MW-CNPs and HT-CNPs were tested for metal ion selectivity in aqueous medium. MW-CNPs showed selectivity for Fe3+ among the tested metal ions and important studies such as for interference, linear range and limit of detection were carried out. The application of MW-CNPs for detection of Fe3+ in water was demonstrated.

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.

Enhanced photocatalytic performance of morphologically tuned Bi2S3 NPs in the degradation of organic pollutants under visible light irradiation.

Here in, morphologically tuned Bi2S3 NPs were successfully synthesized from a single-source precursor complex [Bi(ACDA)3] [HACDA=2-aminocyclopentene-1-dithiocarboxylic acid] by decomposing in various solvents using a simple solvothermal method. The as-obtained products were characterized by XRD, TEM, UV-vis spectroscopy and BET surface area measurements. Structural analyses revealed that the as-prepared Bi2S3 NPs can be tuned to different morphologies by varying various solvents and surfactants. The interplay of factors that influenced the size and morphology of the nanomaterials has been studied. Moreover, mastery over the morphology of nanoparticles enables control of their properties and enhancement of their usefulness for a given application. These materials emerged as a highly active visible light-driven photocatalyst towards degradation of methylene blue dye and the efficiencies are dependent on size and surface area of the NPs. In addition, photocatalytic degradation of highly toxic dichlorodiphenyltrichloroethane was studied using synthesized Bi2S3 NPs as catalyst and the rate of degradation has been found to be much better compared to that exhibited by commercial WO3. We believe that this new synthesis approach can be extended to the synthesis of other metal sulfide nanostructures and open new opportunities for device applications.

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.

Colorimetric and fluorogenic recognition of Hg2+ and Cr3+ in acetonitrile and their test paper recognition in aqueous media with the aid of rhodamine based sensors.

Two new rhodamine derivatives (L1 and L2) were synthesized, characterized and their ion recognition property has been investigated. Both of the ionophores exhibit colorimetric and fluorogenic response for Hg(2+) and Cr(3+) ions among large number of alkali, alkaline earth and transition metal ions tested in acetonitrile. Detail studies on determination of binding constant, binding mode, reversibility of binding, lower detection limit have been carried out. Detection of metal ions in aqueous media has also been demonstrated by preparation of simple, convenient and disposable test paper sensors with two approaches viz. filter paper and membrane filter loaded with these ionophores. Both of these methods responded sharply to both the metal ions (Hg(2+) and Cr(3+)) in aqueous solution, detectable by bared-eye. For better sensing at low concentration of metal ions, reprecipitation followed by filtration enrichment of ligands on membrane filter was employed.

Carboxymethylagarose-AuNPs generated through green route for selective detection of Hg2+ in aqueous medium with a blue shift.

We report here a facile, rapid, cost-effective method via a green route for the selective detection of Hg(2+) in aqueous media. In this study carboxymethylagarose (CMA) is used to generate gold nanoparticles and subsequently to act as a stabilizer for the CMA-functionalized gold nanoparticles (CMA-AuNPs). The resulting CMA-AuNPs was characterized by UV-visible, X-ray diffraction, transmission electron microscopy (TEM), dynamic light scattering (DLS), atomic force microscopy (AFM) and zeta potential measurements. Zeta potential value (∼ -73 mv) of CMA-AuNPs in the aqueous medium shows its higher stability. When CMA-AuNPs were exposed to an aqueous Hg(2+), a blue shift for its localized surface plasmon resonance absorbance (LSPR) band is observed along with significant colour change of the solution. The probe enables to detect Hg(2+) in the range of 0.01-100 ppm even in spiked lake water samples. This study offers a sustainable and eco-friendly route for selective detection of Hg(2+) in aqueous solution and may find potential application towards water purification.

Probing the influence of solvent effect on the lithium ion binding affinity of 12-crown-O3N derivatives with unsaturated side arms: a computational study.

Molecular structures of crown ether derivatives play a crucial role in complexing and transporting alkali metal ions such as lithium ion. The complexation of such ions take place in solution, hence it is important to examine the complexation behavior of host systems in solution. We have investigated employing quantum chemical calculations the stable conformations of 12-crown-O3N derivatives with unsaturated side-arms and its corresponding Li(+) ion complexation in low polar to high polar solvent medium. The General Gradient Approximation (GGA) using PW91 functional with DNP basis set calculated results show that the side-arms contribute via cation-π interaction in the complexation of lithium ion with the receptor molecules 2 and 3 quite effectively in the gas phase and in low polar solvent medium (CHCl3). The vinyl and acetylene groups attached to the receptor molecules are away from the cavity of the crown ether, however, orients toward the cavity while complexing with the lithium ion. The auxiliary effect of such side-arms to augment the binding affinity of Li(+) ion is reduced in the high polar solvent medium. The side-arms also orient away from the complexed Li(+) ion in relatively more polar solvents. These calculated results indicate that the complexing ability of aza-crowns toward the Li(+) ion can be enhanced with the unsaturated side-arms in low polar solvent medium, which however, is less effective in more polar mediums.

Electrocatalytic activity of silver nanoparticles modified glassy carbon electrode as amperometric sensor for hydrogen peroxide.

A simple chemical route has been applied for the preparation of quasi-spherical silver (Ag) nanoparticles (NPs) with average diameter of 265 and 8 nm. The as prepared products were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-vis absorption spectroscopy. Ag NPs immobilized on glassy carbon (GC) electrode showed a superior electrocatalytic activity for the reduction of hydrogen peroxide (H2O2) in aqueous medium. The fabricated electrode was also applied for the amperometric detection of H2O2 and showed a favorable response at an applied potential of -0.5 V (vs. Ag/AgCl). The results demonstrate that the fabricated electrode has potential application for hydrogen peroxide sensor.