Effect of capping agent concentration on thermoluminescence and photoluminescence of copper‐doped zinc sulfide nanoparticles

Copper‐doped zinc sulfide (ZnS:Cu) nanoparticles with varying concentrations of capping agent were prepared using a chemical route technique. These particles were characterized by scanning electron microscopy (SEM), transmission electron microscopy and X‐ray diffraction (XRD). Optical absorption studies showed that the absorption edge shifted towards the blue region as the concentration of the capping agent increased. Using effective mass approximation, calculation of the nanoparticle size indicated that effective band gap energy increases with decreasing particle size. The thermoluminescence (TL) properties of sodium hexameta phosphate (SHMP)‐passivated ZnS:Cu nanoparticles were investigated after UV irradiation at room temperature. The TL glow curve of capped ZnS:Cu showed variations in TL peak position and intensity with the change in capping agent concentration. The photoluminescence (PL) spectra of ZnS:Cu nanoparticles excited at 254 nm exhibited a broad green emission band peaking around 510 nm, which confirmed the characteristic feature of Zn²⁺ as well as Cu²⁺ ions as the luminescent centres in the lattice. The PL spectra of ZnS:Cu nanoparticles with increasing capping agent concentrations revealed that the emission becomes more intense and shifted towards shorter wavelengths as the sizes of the samples were reduced. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of ZnSe and ZnSe:Cu quantum dots by a room temperature photochemical (UV‐assisted) approach using Na2SeO3 as Se source and investigating optical properties

In this study, ZnSe and ZnSe:Cu quantum dots (QDs) were synthesized using Na₂SeO₃ as the Se source by a rapid and room temperature photochemical (UV‐assisted) approach. Thioglycolic acid (TGA) was employed as the capping agent and UV illumination activated the chemical reactions. Synthesized QDs were successfully characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) and UV–visible (UV–vis) spectroscopy, Fourier transform‐infrared (FT‐IR), and energy dispersive X‐ray spectroscopy (EDX). XRD analysis demonstrated the cubic zinc blend phase QDs. TEM images indicated that round‐shaped particles were formed, most of which had a diameter of about 4 nm. The band gap of the ZnSe QDs was higher than that for ZnSe in bulk. PL spectra indicated an emission with three peaks related to the excitonic, surface trap states and deep level (DL) states. The band gap and QD emission were tunable only by UV illumination time during synthesis. ZnSe:Cu showed green emission due to transition of electrons from the Conduction band (CB) or surface trap states to the ²T₂ acceptor levels of Cu²⁺. The emission was increased by increasing the Cu²⁺ ion concentration, such that the optimal value of PL intensity was obtained for the nominal mole ratio of Cu:Zn 1.5%.     

Temperature Driven Plasmon-Exciton Coupling in Thermoresponsive Dextran-Graft-PNIPAM/Au Nanoparticle/CdTe Quantum Dots Hybrid Nanosystem

The temperature-driven plasmon-exciton coupling in thermoresponsive dextran-graft-PNIPAM/Au nanoparticle/CdTe quantum dot (D-g-PNIPAM/Au NPs/CdTe QDs) hybrid nanosystem was studied. A significant (0.84 eV) splitting of the absorption peak was observed in the absorption spectrum of the nanosystem, which reflects the fact of formation of plexcitons, occurring due to strong plasmon-exciton coupling. An increasing with time plasmonic enhancement of the photoluminescence of CdTe QDs was revealed, as a result of the penetration of quantum dots into the volume of the D-g-PNIPAM/Au NP hybrid nanosystem and bonding to it. The heating–cooling cycle of the aqueous solution of the studied nanosystem leads to a reversible quenching-recovery alteration of the QD photoluminescence. The quenching was rationalized as a result of an increased probability of nonradiative resonance energy transfer (RET) from CdTe QDs to Au NPs, which occurs due to shortening of the NP-QD distance, caused by shrinking of the macromolecule due to cooling-induced lower critical solution temperature phase transition. Increasing the NP-QD distance in the heating stage recovers the QD PL intensity. The observed effect opens up opportunities for the controlled reversible temperature-driven tuning of the photoluminescence intensity of D-g-PNIPAM/Au NP/CdTe QD nanosystem, which is highly important for its potential use in photonics and biomedical applications.

     

Fluorescent probe for detection of Cu2+ using core‐shell CdTe/ZnS quantum dots

Core‐shell CdTe/ZnS quantum dots capped with 3‐mercaptopropionic acid (MPA) were successfully synthesized in aqueous medium by hydrothermal synthesis. These quantum dots have advantages compared to traditional quantum dots with limited biological applications, high toxicity and tendency to aggregate. The concentration of Cu²⁺ has a significant impact on the fluorescence intensity of quantum dots (QDs), therefore, a rapid sensitive and selective fluorescence probe has been proposed for the detection of Cu²⁺ in aqueous solution. Under optimal conditions, the fluorescence intensity of CdTe/ZnS QDs was linearly proportional to the concentration of Cu²⁺ in the range from 2.5 × 10^–9 M to 17.5 × 10^–7 M with the limit of 1.5 × 10^–9 M and relative standard deviation of 0.23%. The quenching mechanism is static quenching with recoveries of 97.30–102.75%. Copyright © 2015 John Wiley & Sons, Ltd.     

Nucleation temperature‐controlled synthesis and in vitro toxicity evaluation of l‐cysteine‐capped Mn:ZnS quantum dots for intracellular imaging

Quantum dots (QDs), one of the fastest developing and most exciting fluorescent materials, have attracted increasing interest in bioimaging and biomedical applications. The long‐term stability and emission in the visible region of QDs have proved their applicability as a significant fluorophore in cell labelling. In this study, an attempt has been made to explore the efficacy of l ‐cysteine as a capping agent for Mn‐doped ZnS QD for intracellular imaging. A room temperature nucleation strategy was adopted to prepare non‐toxic, water‐dispersible and biocompatible Mn:ZnS QDs. Aqueous and room temperature QDs with l ‐cysteine as a capping agent were found to be non‐toxic even at a concentration of 1500 µg/mL and have wide applications in intracellular imaging. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of CdSe quantum dots with luminescence in the violet region of the solar spectrum

We have designed a simple, one‐step synthesis of CdSe quantum dots with photoluminescence frequencies ranging from the red through to the violet region of the solar spectrum. The photoluminescence peaks have FWHM of 30 nm indicating absorption over a narrow range of wavelengths. The effect of solvent type and solvent boiling point on the physical and photoluminescence properties of the quantum dots has been studied. High boiling point, non‐polar solvents shift the photoluminescence peak to longer wavelengths and low boiling point, polar solvents shift the photoluminescence peak to shorter wavelengths. Copyright © 2009 John Wiley & Sons, Ltd.     

The size effect to O2−–Ce4+ charge transfer emission and band gap structure of Sr2CeO4

Sr₂CeO₄ phosphors with different crystalline sizes were synthesized by the sol–gel method or the solid‐state reaction. Their crystalline size, luminescence intensity of O^2??Ce⁴⁺ charge transfer and energy gaps were obtained through the characterization by X‐ray diffraction, photoluminescence spectra, as well as UV–visible diffuse reflectance measurements. An inverse relationship between photoluminescence (PL) spectra and crystalline size was observed when the heating temperature was from 1000°C to 1300°C. In addition, band energy calculated for all samples showed that a reaction temperature of 1200°C for the solid‐state method and 1100°C for sol–gel method gave the largest values, which corresponded with the smallest crystalline size. Correlation between PL intensity and crystalline size showed an inverse relationship. Band structure, density of states and partial density of states of the crystal were calculated to analyze the mechanism using the cambrige sequential total energy package (CASTEP) module integrated with Materials Studio software.     

Enhanced chemiluminescence of the fluorescein–KIO4 system by CdTe quantum dots for determination of catechol

In this paper, a novel chemiluminescence (CL) system was introduced based on the use of CdTe quantum dots (QDs) with the mixture solutions of fluorescein and potassium periodate (KIO₄) in alkaline medium. The CL signal of an ultra‐weak system was strongly enhanced in the presence of QDs. The application of CdTe QDs–fluorescein–KIO₄ system is reported for the first time. It was found that catechol had a diminishing effect on the CL reaction. Under optimal experimental conditions, CL intensity decreased linearly in a 1 to 100 μM catechol concentration range, with a 0.18 μM detection limit. A possible reaction mechanism was proposed according to the results of kinetic analyses, CL spectra, ultraviolet–visible and fluorescence spectra. The results pointed to an efficient energy transfer between the CL energy donor CdTe QDs and acceptor fluorescein. Finally, the CL method was successfully applied to the determination of catechol in environmental water samples.     

Plasmonic Tuning of Photoluminescence from Semiconducting Quantum Dot Assemblies

We report tuning of photoluminescence enhancement and quenching from closed packed monolayers of cadmium selenide quantum dots doped with gold nanoparticles. Plasmon-mediated control of the emission intensity from the monolayers is achieved by varying the size and packing density of the quantum dots as well as the doping concentration of gold nanoparticles. We observe a unique packing density dependent crossover from enhancement to quenching and vice versa for fixed size of quantum dots and doping concentration of gold nanoparticles. We suggest that this behavior is indicative of a crossover from single particle to collective emission from quantum dots mediated by gold nanoparticles.     

Rhizopus stolonifer mediated biosynthesis of biocompatible cadmium chalcogenide quantum dots

We report an efficient method to biosynthesize biocompatible cadmium telluride and cadmium sulphide quantum dots from the fungus Rhizopus stolonifer. The suspension of the quantum dots exhibited purple and greenish-blue luminescence respectively upon UV light illumination. Photoluminescence spectroscopy, X-ray diffraction, and transmission electron microscopy confirms the formation of the quantum dots. From the photoluminescence spectrum the emission maxima is found to be 424 and 476 nm respectively. The X-ray diffraction of the quantum dots matches with results reported in literature. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay for cell viability evaluation carried out on 3-days transfer, inoculum 3 × 10⁵ cells, embryonic fibroblast cells lines shows that more than 80% of the cells are viable even after 48 h, indicating the biocompatible nature of the quantum dots. A good contrast in imaging has been obtained upon incorporating the quantum dots in human breast adenocarcinoma Michigan Cancer Foundation-7 cell lines.     

Assembly of light‐emitting diode based on hydrophilic CdTe quantum dots incorporating dehydrated silica gel

Stable photoluminescence QD light‐emitting diodes (QD‐LEDs) were made based on hydrophilic CdTe quantum dots (QDs). A quantum dot‐inorganic nanocomposite (hydrophilic CdTe QDs incorporating dehydrated silica gel) was prepared by two methods (rotary evaporation and freeze drying). Taking advantage of its viscosity, plasticity and transparency, dehydrated silica gel could be coated on the surface of ultraviolet (UV) light LEDs to make photoluminescence QD‐LEDs. This new photoluminescence QD‐LED, which is stable, environmentally non‐toxic, easy to operate and low cost, could expand the applications of hydrophilic CdTe QDs in photoluminescence. Copyright © 2015 John Wiley & Sons, Ltd.     

Adhesive thermosensitive gels for local delivery of viral vectors

Local delivery of viral vectors can enhance the efficacy of therapies by selectively affecting necessary tissues and reducing the required vector dose. Pluronic F127 is a thermosensitive polymer that undergoes a solution–gelation (sol–gel) transition as temperature increases and can deliver vectors without damaging them. While pluronics can be spread over large areas, such as the surface of an organ, before gelation, they lack sufficient adhesivity to remain attached to some tissues, such as the surface of the heart or mucosal surfaces. Here, we utilized blends of pluronic F127 and polycarbophil (PCB), a mucoadhesive agent, to provide the necessary adhesivity for local delivery of viral vectors to the cardiac muscle. The effects of PCB concentration on adhesive properties, sol–gel temperature transition and cytocompatibility were evaluated. Rheological studies showed that PCB decreased the sol–gel transition temperature at concentrations >1% and increased the adhesive properties of the gel. Furthermore, these gels were able to deliver viral vectors and transduce cells in vitro and in vivo in a neonatal mouse apical resection model. These gels could be a useful platform for delivering viral vectors over the surface of organs where increased adhesivity is required.     

An innovative sol–gel naringinase bioencapsulation process for glycosides hydrolysis

In this work, a biocatalytic system was chosen to enable the deglycosylation of natural glycosides in order to improve their biological activity. Naringinase, which has both alpha-l-rhamnosidase and beta-d-glucosidase activities, was the enzyme used. Naringin, the glycoside substrate used in this bioconversion, and its aglycone product naringenin are compounds with interesting pharmacological activities such as anti-oxidant and anti-inflammatory; naringenin also acts as an anti-carcinogenic and neuroprotective agent, demonstrating a high potential for use by the pharmaceutical industry.Sol–gel, an innovative technique performed in aqueous media, was developed for naringinase immobilization in lens-shaped particles. Different sol–gel precursors, including tetramethoxysilane (TMOS), methyltrimethoxysilane (MTS), 3-aminopropyltrimethoxysilane (APS) and diglycerylsilane (DGS) with different aging times were tested in five consecutive trials. The best results were obtained with TMOS and TMOS/DGS after 4 h aging time and TMOS/glycerol and DGS at 14 h aging time. The characterization of these matrices was performed with respect to their diameter, volume, naringin and naringenin partition coefficients, and the optimum temperature and pH for naringinase activity. The operational stability of the bioencapsulated naringinase in the selected sol–gel matrices was studied through successive reutilizations. The naringinase sol–gel matrix (TMOS, DGS and TMOS/DGS) deactivation studies followed the Sadana model. The matrix TMOS/glycerol showed a constant 100% residual activity after 50 consecutive runs.     

Plasmonic Effect Enhancement in Ridge–Trench Structure Assisted by Fluorescence Dye

Confinement of exciton–polaritons using ridge–trench structures filled with fluorescent dye materials was investigated on the basis of geometrical analysis as well as plasmonic behavior analysis. It was found that the photoluminescence intensity of the dye increased significantly in the trench than on the ridge due to geometry confinement. However, with silver layer deposited between the ridge–trench structure on Si substrate and the fluorescence dye, apparent photoluminescence peaks due to surface plasmon resonance centered at 360 nm (3.45 eV) were generated while the photoluminescence peaks of the dye materials centered at 580 nm (2.14 eV) quenched in the trench. Competition of spontaneous emission coupled into external electromagnetic modes and plasmon modes is the cause for the quench in photoluminescence. Our results show a direct energy transfer from low-energy photoluminescence to higher energy photoluminesence in dye materials due to plasmonic resonance effects.     

Study of photoluminescence characteristics of CdSe quantum dots hybridized with Cu nanowires

The photoluminescence (PL) characteristics of semiconductor CdSe quantum dots (QDs) aggregated on Cu nanowires (NWs) were studied in detail. The PL relaxation dynamic data show that Cu NWs improve the PL intensity of CdSe QDs by accelerating the emission relaxation rate. The temperature‐dependent PL data and excitation intensity‐dependent PL data suggest that the activation energy of CdSe QDs might decrease due to the excellent heat transfer properties and the plasmon effect of Cu NWs. Copyright © 2016 John Wiley & Sons, Ltd.     

Structural and luminescent studies of erbium‐doped CaZrO3 green‐emitting nanophosphors

Erbium (Er) (0.5, 1.0 and 1.5 wt%)‐doped CaZrO₃ nanophosphors were synthesized by the sol–gel method using poly(vinyl alcohol) as the chelating agent. Their structural and photoluminescence properties were studied using X‐ray diffraction (XRD), field emission scanning electron microscopy–energy dispersive spectroscopy (FESEM‐EDS), transmission electron microscopy (TEM), photoluminescence and Fourier transform infrared spectroscopy (FTIR). The XRD patterns of the samples confirm that nanoscale crystallite sizes. Agglomeration of the samples was observed using field emission scanning electron microscopy images. Energy dispersive spectroscopy measurements confirmed the existence of Ca, Zr, O and Er in the samples. Average particle sizes for the samples were calculated from transmission electron microscopy images. FTIR spectra clearly show characteristic absorption bands related to the metal oxides, as well as some other organic molecules. The photoluminescence spectra show bands in the green region. The Commission International de l'Eclairage coordinates were calculated and found to be in green region.     

Application of Solanum lycopersicum (tomato) hairy roots for production of passivated CdS nanocrystals with quantum dot properties

Semiconductor quantum dot particles have a wide range of applications in medicine, bioassays, computing and photovoltaics. Biological synthesis is an attractive approach for mass production of quantum dots as cells have the capacity to passivate the particles with organic ligands. In this work, hairy roots of Solanum lycopersicum (tomato) were used to produce CdS nanoparticles with quantum dot properties. Treatment of the roots with 100 μM Cd during the mid-growth phase of batch culture elicited cellular responses for Cd detoxification without affecting root growth. A combination of freeze-drying and freeze-thawing of the roots was used to extract Cd from the biomass; anion-exchange chromatography was then applied to selectively remove metal–phytochelatin complexes. Size-fractionation using gel filtration allowed the recovery of phytochelatin-capped Cd- and inorganic sulphide-containing nanoparticles displaying the size and size-dependent optical/electronic properties of CdS quantum dots. At 4–10 nm in diameter, these particles fluoresced at wavelengths corresponding to blue-violet on the colour spectrum and exhibited a high level of photostability with prolonged excitation. Whereas 69% of the Cd extracted from the roots was associated with phytochelatin peptides, the maximum yield of CdS nanocrystals with quantum dot properties was 1.4% of the total Cd taken up into the biomass. This work demonstrates a new culture-based approach for the biosynthesis of metallo-organic semiconductor quantum dots using hairy roots.     

Examination of the stability of hydrophobic (CdSe)ZnS quantum dots in the digestive tract of rats.

Semiconductor quantum dots show promise as alternatives to organic dyes for biological labelling because of their bright and stable photoluminescence. The typical quantum dots is CdSe because colloidal synthesis for nanocrystals of this semiconductor is well established. CdSe is usually passivated with zinc sulfide. While the cytotoxicity of bulk CdSe is well documented, questions about (CdSe)ZnS potential toxicity and behaviour in vivo remain unanswered. The distribution and stability of (CdSe)ZnS quantum dots in Wistar line rats' digestive tract were investigated. Hydrophobic quantum dots were mixed with fat or sonificated in water and administered orally. The distribution and stability of quantum dots moving through the digestive system of rats was followed by fluorescence spectroscopy. In both ways prepared quantum dots were degraded in the digestive tract of animals. Quantum dots mixed with fat were more stable and degraded more slowly than quantum dots sonificated in water. The data obtained suggest possible toxicity of (CdSe)ZnS quantum dots due to the liberation of Cd(2+).     

Investigating the effect of Zn doping and temperature on the photoluminescence behaviour of CuLaSe2 quantum dots

In this study, CuLaSe₂ and ZnCuLaSe₂ quantum dots (QDs) with a mean size of ~4 nm were synthesized and characterized, and their temperature-dependent photoluminescence (PL) properties were studied in the temperature range from 90 to 300 K for the first time. The results show that the obtained QDs were spherical and revealed excitonic band gaps. The PL intensity for both types of materials decreased when increasing the temperature to 300 K, which was attributed to the nonradiative relaxation and thermal escape mechanisms. As the temperature was increased, the PL linewidths broadened, and PL peak energies were red shifted for both types of QDs due to the exciton–phonon coupling and lattice deformation potential mechanisms. In addition, we found that as the temperature was decreased, the PL spectrum of ZnCuLaSe₂ QDs contained two extra components, which could be attributed to the shallow defect sites (low energy peak) and the crystal phase transition process (high energy peak). The spectrum of CuLaSe₂ QDs contained one extra component, which could be attributed to the crystal phase transition process.     

Photoluminescent properties of novel design heteroleptic Zn(II) complexes

Three novel heteroleptic Zn(II) complexes containing 8‐hydroxy quinoline and various pyrazolone‐based derivatives were synthesized and their structures confirmed by ¹H–nuclear magnetic resonance, mass spectrometry, Fourier transform infra‐red spectroscopy, UV–vis analysis and element analysis. All three complexes showed good photoluminescence properties in the solid state and in solution in the maximum emission range from 475 to 490 nm with a quantum yield of 0.45 to 0.51. Absorption spectra revealed that the complexes possessed a maximum absorption range of 272–281 nm with a band gap of 2.59–2.68 eV. The highest occupied molecular orbital and lowest unoccupied molecular orbital of all the complexes were determine by cyclic voltammetry. All complexes displayed high thermal stability. These characteristics were assessed to find suitability for an alternative cheap light emitter for organic light‐emitting diodes.