Theoretical and experimental investigation of doping M in ZnSe (M = Cd,Mn, Ag,Cu) clusters: optical and bonding characteristics

The optical and bonding characteristics of doping ZnSe quantum dots (QDs) were investigated. Cd‐, Mn‐, Ag‐ and Cu‐doped ZnSe were synthesized in aqueous solution. Theoretically, the intensity of the Cd–Se bond was similar to that of the Zn–Se bond, which illustrates that Cd can be doped into ZnSe materials at any ratio. We found that Mn–Se bonding was stronger than Zn–Se bonding. Ag‐doped ZnSe nanoclusters show the same bonding and configuration as Cu‐doped ZnSe. Moreover, Cd can be doped into ZnSe using both the substitution‐ and vacancy‐doping method. For Mn‐doped ZnSe clusters, small amounts of Mn impurity lead to stronger bonding with Se, but larger amounts of Mn impurity led to the formation of a Mn–Mn metal bond. The theoretical results show that it is difficult to form a vacancy‐doping cluster for Mn‐doped ZnSe materials. In experiments, the absorption and photoluminescence (PL) spectral wavelengths of Mn‐doped ZnSe nanocrystals were the same as those of pure ZnSe nanocrystals, showing that the Mn impurity is not doped into ZnSe nanocrystals. Ag‐ and Cu‐doped ZnSe nanocrystals have the same PL characteristics. The doping of an impurity is related to the solubility product, and not the bonding intensity. Copyright © 2015 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%.     

Significant improvement in photoluminescence of ZnSe(S) alloyed quantum dots prepared in high pH solution

In this paper, we described a simple approach for aqueous synthesis of highly luminescent ZnSe(S) alloyed quantum dots (QDs) in the presence of 3‐mercaptopropionic acid as stabilizers using zinc chloride and NaHSe as precursors. The synthesis conditions were systematically investigated. We observed that the pH value of the Zn precursor solution had significant influence on the optical properties and the structure of the as‐prepared ZnSe(S) QDs. The optimal pH value and molar ratio of Zn²⁺ to HSe^? were 12.0 and 25 : 1 respectively. Under the optimal conditions, we prepared highly photoluminescent ZnSe(S) QDs at up to 31% quantum yield (compared with Rhodamine 6G). The characterization of HRTEM and XRD showed that the ZnSe(S) QDs had good monodispersity and nice crystal structure. The fluorescence life time spectra demonstrated that ZnSe(S) QDs had a long lifetime in contrast to fluorescent dyes. Compared with the currently used organometallic approach, our method was ‘green’, the reaction condition was mild and the as‐prepared ZnSe(S) QDs were water‐soluble. More importantly, our method was low cost, and was very suitable for large‐scale synthesis of highly luminescent ZnSe(S) QDs for the future applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Sensitization enhancement of europium in ZnSe/ZnS core/shell quantum dots induced by efficient energy transfer

Eu‐doped ZnSe:/ZnS quantum dots (formed as ZnSe:Eu/ZnS QDs) were successfully synthesized by a two‐step wet chemical method: nucleation doping and epitaxial shell growing. The sensitization characteristics of Eu‐doped ZnSe and ZnSe/ZnS core/shell QD are studied in detail using photoluminescence (PL), PL excitation spectra (PLE) and time‐resolved PL spectroscopy. The emission intensity of Eu ions is enhanced and that of ZnSe QDs is decreased, implying that energy was transferred from the excited ZnSe host materials (the donor) to the doped Eu ions (the acceptor). PLE reveals that the ZnSe QDs act as an antenna for the sensitization of Eu ions through an energy transfer process. The dynamics of ZnSe:Eu/ZnS core/shell quantum dots with different shell thicknesses and doping concentrations are studied via PL spectra and fluorescence lifetime spectra. The maximum phosphorescence efficiency is obtained when the doping concentration of Eu is approximately 6% and the sample showed strong white light under ultraviolet lamp illumination. By surface modification with ZnS shell layer, the intensity of Eu‐related PL emission is increased approximately three times compared with that of pure ZnSe:Eu QDs. The emission intensity and wavelength of ZnSe:Eu/ZnS core/shell quantum dots can be modulated by different shell thickness and doping concentration. The results provide a valuable insight into the doping control for practical applications in laser, light‐emitting diodes and in the field of biotechnology. Copyright © 2014 John Wiley & Sons, Ltd.     

Indication of intracellular physiological pH changes by l-cysteine-coated CdTe quantum dots with an acute alteration in emission color

A novel quantum dots (QDs) based biosensor was developed to monitor physiological pH changes in both fixed and living cells by means of pH-dependent emission color of the QDs. In our system, the nominally single-sized colloidal solution samples of the l-cysteine-capped CdTe QDs with intrinsically broadened size distributions were prepared by employing aqueous synthesis technique. The quench of fluorescence intensities of the QDs with a 16 nm red shift of the emission maximum and a color change from green to yellow was observed with a slight pH decrease (from 7.0 to 6.8) in the system. This pH-dependent emission could be attributed to the efficient exciton energy transfer from smaller QDs to larger ones, which was controlled by electrostatic-tuned aggregation/disaggregation (low/high pH values) processes of the QDs. In addition to high stability, the emission shift of the QDs was reversible for at least one cycle under optimal conditions. Our pH biosensor may find potential application for monitoring the intracellular pH changes in both physiological and pathological conditions.     

Indication of intracellular physiological pH changes by L-cysteine-coated CdTe quantum dots with an acute alteration in emission color

A novel quantum dots (QDs) based biosensor was developed to monitor physiological pH changes in both fixed and living cells by means of pH-dependent emission color of the QDs. In our system, the nominally single-sized colloidal solution samples of the L-cysteine-capped CdTe QDs with intrinsically broadened size distributions were prepared by employing aqueous synthesis technique. The quench of fluorescence intensities of the QDs with a 16 nm red shift of the emission maximum and a color change from green to yellow was observed with a slight pH decrease (from 7.0 to 6.8) in the system. This pH-dependent emission could be attributed to the efficient exciton energy transfer from smaller QDs to larger ones, which was controlled by electrostatic-tuned aggregation/disaggregation (low/high pH values) processes of the QDs. In addition to high stability, the emission shift of the QDs was reversible for at least one cycle under optimal conditions. Our pH biosensor may find potential application for monitoring the intracellular pH changes in both physiological and pathological conditions.     

Synthesis of glutathione-capped CdS quantum dots and preliminary studies on protein detection and cell fluorescence image.

A series of glutathione (GSH)-capped aqueous CdS quantum dots (QDs) with strong photoluminescence (PL) were prepared by changing the reaction temperatures and times on the basis of optimization of the mole ratio of S to Cd. The reaction time was shortened to about 1/10 compared with that reported previously by increasing the reaction temperature. The absorption and fluorescence spectra indicated good optical properties with PL full width of half-maximum (FWHM) of about 100 nm. The excitation spectrum was broad and continuous in the range 200-480 nm. The PL quantum efficiency (QE) of the prepared QDs was about 36% compared with rhodamine 6G (95%). The shape and size of the CdS QDs were characterized using high-resolution transmission electron microscopy (HRTEM). The prepared QDs were conjugated with bovine serum albumin (BSA) and onion inner pellicle cells and used as fluorescence probes for the first time. The results demonstrated that the fluorescence of CdS can be enhanced by BSA and the enhanced fluorescence intensity is proportional to the concentration of BSA in the range 1.0-10 mg/L. The aggregation of CdS in onion inner pellicle cells and its fluorescence images indicated that the QDs can aggregate around cells soaked for 8 h in CdS solution but enter the interior of cells and become aggregated to the nucleus when they are soaked in CdS solution for longer, e.g. 98 h.     

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.     

Highly luminescent CdTe/CdS/ZnO core/shell/shell quantum dots fabricated using an aqueous strategy

To create core/shell/shell quantum dots (QDs) with high stability against a harmful chemical environment, CdTe/CdS QDs were coated with a ZnO shell in an aqueous solution. An interfaced CdS layer sandwiched between a CdTe core and ZnO shell provided relaxation of the strain at the core/shell interface since lattice parameters of CdS are intermediate between those of CdTe and ZnO. The photoluminescence (PL) peak wavelength of the core/shell/shell QDs was shifted from 569 to 615 nm by adjusting the size of CdTe cores and thickness of CdS and ZnO shells, along with the highest PL quantum yield of the core/shell/shell QDs reaching 80%, which implies promising applications in the field of biomedical labeling. Due to the decrease of surface defects, it was observed that PL lifetimes significantly increased at room temperature as follows: 29.6 34.2, and 47.5 ns for CdTe (537 nm), CdTe/CdS (555 nm) and CdTe/CdS/ZnO (581 nm) QDs, respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of concentration and shell thickness on the optical behavior of aqueous CdTe/ZnSe core/shell quantum dots (QDs) exposed to ionizing radiation

In this work CdTe/ZnSe core/shell quantum dots (QDs) were synthesized via a simple, rapid and room temperature photochemical approach. Optical properties of aqueous prepared CdTe/ZnSe QDs were studied systematically under gamma irradiation with dose range of 0 Gy to 20 kGy. The obtained results showed a regular red shift behavior versus gamma irradiation dose, in photoluminescence peak and absorption edge of the CdTe/ZnSe QDs. Structural properties of CdTe/ZnSe QDs before and after gamma irradiation were characterized by means of X-ray diffraction (XRD), Raman and Fourier-transform infrared (FT-IR) analyses. The obtained results showed that the crystalline structure of CdTe/ZnSe core/shell QDs did not change after gamma irradiation. Concentration and shell thickness as two important factors on the sensitivity of CdTe/ZnSe QDs in front of gamma irradiation have been investigated. Based on this study, CdTe/ZnSe QDs are suggested as good candidates for gamma dosimeter.     

Enantioselective cytotoxicity of ZnS:Mn quantum dots in A549 cells

Chirality strongly influences many biological properties of materials, such as cell accumulation, enzymatic activity, and toxicity. In the past decade, it has been shown that quantum dots (QDs), fluorescent semiconductor nanoparticles with unique optical properties, can demonstrate optical activity due to chiral ligands bound on their surface. Optically active QDs could find potential applications in biomedical research, therapy, and diagnostics. Consequently, it is very important to investigate the interaction of QDs capped with chiral ligands with living cells. The aim of our study was to investigate the influence of the induced chirality of Mn‐doped ZnS QDs on the viability of A549 cells. These QDs were stabilized with D‐ and L‐cysteine using a ligand exchange technique. The optical properties of QDs were studied using UV–Vis, photoluminescence (PL), and circular dichroism (CD) spectroscopy. The cytotoxicity of QDs was investigated by high content screening analysis. It was found that QDs stabilized by opposite ligand enantiomers, had identical PL and UV–Vis spectra and mirror‐imaged CD spectra, but displayed different cytotoxicity: QDs capped with D‐cysteine had greater cytotoxicity than L‐cysteine capped QDs.     

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.     

Aqueous synthesis of CdTe/CdS/ZnS quantum dots and their optical and chemical properties

In this paper, we described a strategy for synthesis of thiol‐coated CdTe/CdS/ZnS (core–shell–shell) quantum dots (QDs) via aqueous synthesis approach. The synthesis conditions were systematically optimized, which included the size of CdTe core, the refluxing time and the number of monolayers and the ligands, and then the chemical and optical properties of the as‐prepared products were investigated. We found that the mercaptopropionic acid (MPA)‐coated CdTe/CdS/ZnS QDs presented highly photoluminescent quantum yields (PL QYs), good photostability and chemical stability, good salt tolerance and pH tolerance and favorable biocompatibility. The characterization of high‐resolution transmission electron microscopy (HRTEM), X‐ray powder diffraction (XRD) and fluorescence correlation spectroscopy (FCS) showed that the CdTe/CdS/ZnS QDs had good monodispersity and crystal structure. The fluorescence life time spectra demonstrated that CdTe/CdS/ZnS QDs had a longer lifetime in contrast to fluorescent dyes and CdTe QDs. Furthermore, the MPA‐stabilized CdTe/CdS/ZnS QDs were applied for the imaging of cells. Compared with current synthesis methods, our synthesis approach was reproducible and simple, and the reaction conditions were mild. More importantly, our method was cost‐effective, and was very suitable for large‐scale synthesis of CdTe/CdS/ZnS QDs for future applications. Copyright © 2010 John Wiley & Sons, Ltd.     

Spontaneous emission of semiconductor quantum dots in inverse opal SiO2 photonic crystals at different temperatures

The photoluminescence (PL) characteristics of CdSe quantum dots (QDs) infiltrated into inverse opal SiO₂ photonic crystals (PCs) are systemically studied. The special porous structure of inverse opal PCs enhanced the thermal exchange rate between the CdSe QDs and their surrounding environment. Finally, inverse opal SiO₂ PCs suppressed the nonlinear PL enhancement of CdSe QDs in PCs excited by a continuum laser and effectively modulated the PL characteristics of CdSe QDs in PCs at high temperatures in comparison with that of CdSe QDs out of PCs. The final results are of benefit in further understanding the role of inverse opal PCs on the PL characteristics of QDs. Copyright © 2015 John Wiley & Sons, Ltd.     

Tunable excitation properties of ZnCdS:Mn/ZnS quantum dots for cancer imaging

Water‐soluble ZnS:Mn quantum dots (QDs) were synthesized using a hydrothermal method with 3‐mercaptopropionic acid as stabilizer. The optical properties of ZnS:Mn QDs were thoroughly investigated by tuning the doping concentration of Mn²⁺ and the Zn/S precursor ratio, to obtain an optimal parameter for QDs with excellent fluorescence characteristics. ZnS:Mn QDs excited at only one wavelength, however, which seriously limited their further application. Here, a trace Cd ion was doped into a ZnS host, resulting in QD excitation covering a wide adjustable waveband. Furthermore, when a ZnS shell was coated onto the surface of the ZnCdS:Mn QDs, photoluminescence intensity and stability were further enhanced. After coupling with an anti‐CK 19 antibody, the ZnCdS:Mn/ZnS core/shell QDs were able to function by labeling cancer cells, indicating that they could be considered as a suitable bio‐probe for cells and tissue imaging.     

Ferrous iron uptake by Bifidobacterium bifidum var. pennsylvanicus: the effect of metals and metabolic inhibitors

Ferrous iron uptake studies in Bifidobacterium bifidum var. pennsylvanicus were carried out in a well-defined salt solution termed "modified Hanks solution" at both high iron concentrations (LAFIUS conditions) and low concentrations (HAFIUS conditions). Various divalent metals, Mn2+, Zn2+, Ni2+ and Cu2+, inhibited iron uptake under HAFIUS conditions in a non-competitive manner, and in a pseudo-competitive manner under LAFIUS conditions. Cr2+ had no effect. Co2+ inhibited iron uptake competitively under HAFIUS conditions. Metabolic affectors that inhibited iron uptake both under HAFIUS and LAFIUS conditions were: tetraphenylphosphonium chloride, diethylstilbesterol, vanadate, carbonylcyanide-m-chlorophenyl-hydrazone, and a mixture of valinomycin and nigericin. Substances that stimulated iron uptake were KCl, valinomycin, and nigericin. Iron uptake under LAFIUS conditions in piperazine-buffered modified Hanks solution was higher than that in the acetate-buffered solution, and acetate inhibited iron uptake in the piperazine buffer. HAFIUS showed no difference. It is concluded that iron uptake in bifidobacteria is driven by an ATPase-dependent proton-motive force and that both the pH gradient and membrane potential are involved in this process. Mn2+, Zn2+, Ni2+, and Cu2+ may be transported via LAFIUS, but not HAFIUS. HAFIUS may transport only Co2+ in addition to Fe2+.     

Bright solid‐state luminescence of green‐red tunable CdTe@BaCO3 composite: Synthesis and properties

Realizing efficient solid‐state luminescence is of great important to expand quantum dots (QDs) application fields. This work reports the preparation of CdTe@BaCO₃ composite by a one‐pot precipitation method. Both steady‐state PL and PL decay characteristics in either solid‐state or colloid solution show no obvious difference, mainly benefited from the effective protection of BaCO₃ on QDs from the external environment. By utilizing green and red CdTe QDs as dual‐color emission centers, precise emitting‐color control from green (0.312, 0.667) to red (0.691, 0.292) could be achieved in CdTe@BaCO₃ composite by adjusting volume ratio of CdTe solution precursor. Our results demonstrate that this composite material shows bright solid‐state luminescence and facile adjustment of the emitting color in QDs‐based composite is feasible, which could offer new path to design color‐tunable luminescent materials for future optoelectronic applications.     

Quantum dots‐based fluorescence resonance energy transfer biosensor for monitoring cell apoptosis

The development of advanced methods for accurately monitoring cell apoptosis has extensive significance in the diagnostic and pharmaceutical fields. In this study, we developed a rapid, sensitive and selective approach for the detection of cell apoptosis by combining the site‐specific recognition and cleavage of the DEVD–peptide with quantum dots (QDs)‐based fluorescence resonance energy transfer (FRET). Firstly, biotin‐peptide was conjugated on the surface of AuNPs to form AuNPs‐pep through the formation of an Au‐S bond. Then, AuNPs–pep–QDs nanoprobe was obtained through the connection between AuNPs–pep and QDs. FRET is on and the fluorescence of QDs is quenched at this point. The evidence of UV–vis spectra, transmission electron microscopy (TEM), and Fourier transform infrared (FT‐IR) spectroscopy revealed that the connection was successful. Upon the addition of apoptosis cell lysis solution, peptide was cleaved by caspase‐3, and AuNPs was dissociated from the QDs. At this time, FRET is off, and thus the QDs fluorescence was recovered. The experimental conditions were optimized in terms of ratio of peptide to AuNPs, buffer solution, and the temperature of conjugation and enzyme reaction. The biosensor was successfully applied to distinguishing apoptosis cells and normal cells within 2 h. This study demonstrated that the biosensor could be utilized to evaluate anticancer drugs.     

Synthesis of highly luminescent and biocompatible CdTe/CdS/ZnS quantum dots using microwave irradiation: a comparative study of different ligands

We compared the effects of several ligands frequently used in aqueous synthesis, including L‐cysteine, L‐cysteine hydrochloride, N‐acetyl‐L‐cysteine (NAC), glutathione and 3‐mercaptopropionic acid, for microwave synthesis of CdTe quantum dots (QDs) in a sealed vessel with varied temperatures and times, and then developed a rapid microwave‐assisted protocol for preparing highly luminescent, photostable and biocompatible CdTe/CdS/ZnS core–multishell QDs. The effects of molecular structures of these ligands on QD synthesis under high temperatures were explored. Among these ligands, NAC was found to be the optimal ligand in terms of the optical properties of resultant QDs and reaction conditions. The emission wavelength of NAC‐capped CdTe QDs could reach 700 nm in 5 min by controlling the reaction temperature, and the resultant CdTe/CdS/ZnS core–multishell QDs could achieve the highest quantum yields up to 74% with robust photostability. In addition, the effects of temperature, growth time and shell–precursor ratio on shell growth were examined. Finally, cell culturing indicated the low cytotoxicity of CdTe/CdS/ZnS core–multishell QDs as compared to CdTe and CdTe/CdS QDs, suggesting their high potential for applications in biomedical imaging and diagnostics. Copyright © 2014 John Wiley & Sons, Ltd.     

Biosorption of chromium, copper, manganese and zinc by Pseudomonas aeruginosa AT18 isolated from a site contaminated with petroleum

The study describes the sorption of Cr, Cu, Mn and Zn by Pseudomonas aeruginosa AT18 isolated from a site contaminated with petroleum and heavy metals. The concentrations studied were 50, 49, 60 and 70 (mg L(-1)) for Cr, Cu, Mn and Zn, respectively. The solution pH and ionic strength were very important factors in the metal biosorption performance and the biosorption capacity of P. aeruginosa AT18 for Cr3+,Cu2+, Mn2+ and Zn2+. In aqueous solution, the biosorption increased with increasing pH in the range 5.46-7.72. The results obtained in the experimental assays show that P. aeruginosa AT18 has the capacity for biosorption of the metallic ions Cr3+, Cu2+ and Zn2+ in solutions, although its capacity for the sorption of manganese is low (22.39 mg Mn2+/g of biomass) in comparison to the Cr3+, Cu2+ and Zn2+ ions, as shown by the individual analyses. However, 20% of the manganese was removed from an initial concentration of 49.0 mg L(-1), with a Qm value similar to that obtained in solutions containing mixtures of Cr3+, Cu2+, Mn2+and Zn2+. The chromium level sorbed by P. aeruginosa AT18 biomass was higher than that for Cu, Mn and Zn, with 100% removal in the pH range 7.00-7.72 and a Qm of 121.90-200.00 mg of Cr3+/g of biomass. The removal of Cr, Cu and Zn is also a result of precipitation processes.