Synthesis,effect of capping agents and optical properties of manganese‐doped zinc sulphide nanoparticles

Mn²⁺‐doped ZnS nanoparticles have been successfully synthesized by a chemical precipitation method, using non‐ionic surfactants such as PMMA and PEG. The particles were prepared in an air atmosphere at 80°C. X‐ray diffraction (XRD), transmission electron microscopy (TEM), UV‐visible and photoluminescence (PL) studies were used to investigate the effect of the capping agent on the size, morphology and optical properties of the ZnS–Mn²⁺ nanoparticles. Enhanced PL was observed from the surfactant‐capped ZnS–Mn²⁺ nanoparticles. The PL spectra showed a broad blue emission band in the range 460–445 nm and a Mn²⁺‐related yellow‐orange emission band in the range 581–583 nm. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Tuneable luminescence properties of EDTA‐assisted ZnS:Mn nanocrystals from a yellow‐orange to a red emission band

Luminescence technology has been improved with the help of semiconductor nanoparticles that possess novel optical and electrical properties compared with their bulk counterpart. The aim of this study was to design semiconductor nanocrystals in their pure (ZnS) or doped form (ZnS:Mn) with different concentrations of Mn²⁺ ions by a wet chemical route stabilized by ethylenediamine tetra‐acetic acid (EDTA) and to evaluate their luminescence properties. The nanocrystals were characterized by physicochemical techniques such as X‐ray diffraction (XRD), High‐resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SEAD), EDS, and ultraviolet (UV)–visible light and photoluminescence (PL) studies. These results showed the presence of cubic phase and spherically shaped nanocrystals. A blue shift with respect to their bulk counterpart was observed. PL emission spectra were observed with a fixed blue peak and the yellow‐orange bands were red shifted towards the red region under the same excitation wavelength. The orange‐red bands were attributed to the radiation transition of electrons in 3d5 unfilled shells of Mn²⁺ ions [⁴T₁(⁴G)‐⁶A₁(⁶S)]; the ZnS matrix varied with Mn²⁺ concentration. Shift and increase in the intensity of the PL and absorption bands were observed with increase in Mn content. The study showed that Mn²⁺‐doped ZnS nanocrystal emission bands can be tuned from the yellow‐orange to the red regions under a controlled synthesis process and could be used as promising luminescent emitters in the biology field upon functionalization with suitable materials. Further studies on construction with various other materials will be useful for practical applications.     

Luminescence study of monodispersed ZnS nanoparticles

Monodispersed ZnS nanoparticles have been successfully synthesized by a chemical precipitation method in an air atmosphere using polyvinylpyrrolidone (PVP) and sodium hexametaphosphate (SHMP) as surfactants. The synthesized nanoparticles were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FT‐IR), UV–Vis optical absorption and photoluminescence (PL) spectra. Prepared surfactants capped ZnS nanoparticles are highly homogeneous and well dispersed. Optical absorption spectra showed a strong blue shift from the uncapped particles due to the quantum confinement effect. The capped ZnS emission intensity is enhanced than more the uncapped particles. The size of the synthesized particles is around 4–6.5 nm range. Copyright © 2012 John Wiley & Sons, Ltd.     

Eu2+‐induced enhancement of defect luminescence of ZnS

The Eu²⁺‐induced enhancement of defect luminescence of ZnS was studied in this work. While photoluminescence (PL) spectra exhibited 460 nm and 520 nm emissions in both ZnS and ZnS:Eu nanophosphors, different excitation characteristics were shown in their photoluminescence excitation (PLE) spectra. In ZnS nanophosphors, there was no excitation signal in the PLE spectra at the excitation wavelength λ_ex > 337 nm (the bandgap energy 3.68 eV of ZnS); while in ZnS:Eu nanophosphors, two excitation bands appeared that were centered at 365 nm and 410 nm. Compared with ZnS nanophosphors, the 520 nm emission in the PL spectra was relatively enhanced in ZnS:Eu nanophosphors and, furthermore, in ZnS:Eu nanophosphors the 460 nm and 520 nm emissions increased more than 10 times in intensity. The reasons for these differences were analyzed. It is believed that the absorption of Eu²⁺ intra‐ion transition and subsequent energy transfer to sulfur vacancy, led to the relative enhancement of the 520 nm emission in ZnS:Eu nanophosphors. In addition, more importantly, Eu²⁺ acceptor‐bound excitons are formed in ZnS:Eu nanophosphors and their excited levels serve as the intermediate state of electronic relaxation, which decreases non‐radiative electronic relaxation and thus increases the intensity of the 460 nm and 520 nm emission dramatically. In summary, the results in this work indicate a new mechanism for the enhancement of defect luminescence of ZnS in Eu²⁺‐doped ZnS nanophosphors. Copyright © 2016 John Wiley & Sons, Ltd.     

Optical and structural characterization of CdS/ZnS and CdS:Cu2+/ZnS core–shell nanoparticles

Core‐shell CdS/ZnS (Zn 0.025?0.125 M) and CdS:Cu²⁺(1%)/ZnS nanoparticles were successfully synthesized using a chemical method. X‐ray diffraction (XRD), high‐resolution transmission electron microscopy (HR TEM), photoluminescence (PL) and UV/Visible (UV/Vis) techniques were used to characterize the novel CdS/ZnS and CdS:Cu²⁺/ZnS core–shell nanoparticles. All absorption peaks of the synthesized samples were highly blue‐shifted from the bulk CdS and ZnS. Very narrow and symmetric PL emission was observed in the yellow region for core–shell CdS/ZnS. Furthermore, the PL emission of CdS/ZnS was tuned into orange region by incorporate the Cu ion into the core CdS lattice. Copyright © 2013 John Wiley & Sons, Ltd.     

Copper nanocluster‐enhanced luminol chemiluminescence for high‐selectivity sensing of tryptophan and phenylalanine

A remarkable method for the highly sensitive detection of phenylalanine and tryptophan based on a chemiluminescence (CL) assay was reported. It was found that fluorescent copper nanoclusters capped with cysteine (Cys‐CuNCs) strongly enhance the weak CL signal resulting from the reaction between luminol and H₂O₂. Of the amino acids tested, phenylalanine and tryptophan could enhance the above CL system sensitively. Under optimum conditions, this method was satisfactorily described by a linear calibration curve over a range of 1.0 × 10^?6 to 2.7 × 10^?5 M for phenylalanine and 1.0 × 10^?7 to 3.0 × 10^?5 M for tryptophan, respectively. The effect of various parameters such as Cys‐CuNC concentration, H₂O₂ concentration and pH on the intensity of the CL system were also studied. The main experimental advantage of the proposed method was its selectivity for two amino acids compared with others. To evaluate the applicability of the method to the analysis of a real biological sample it was used to determine tryptophan and phenylalanine in human serum and remarkable results were obtained.     

Synthesis,characterization and optical properties of polymer‐based ZnS nanocomposites

Nanostructured polymer–semiconductor hybrid materials such as ZnS–poly(vinyl alcohol) (ZnS–PVA), ZnS–starch and ZnS–hydroxypropylmethyl cellulose (Zns–HPMC) are synthesized by a facile aqueous route. The obtained nanocomposites are characterized using various techniques such as X‐ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), UV/vis spectroscopy and photoluminescence (PL). XRD studies confirm the zinc blende phase of the nanocomposites and indicate the high purity of the samples. SEM studies indicate small nanoparticles clinging to the surface of a bigger particle. The Energy Dispersive Analysis by X‐rays (EDAX) spectrum reveals that the elemental composition of the nanocomposites consists primarily of Zn:S. FTIR studies indicate that the polymer matrix is closely associated with ZnS nanoparticles. The large number of hydroxyl groups in the polymer matrix facilitates the complexation of metal ions. The absorption spectra of the specimens show a blue shift in the absorption edge. The spectrum reveals an absorption edge at 320, 310 and 325 nm, respectively. PL of nanocomposites shows broad peaks in the violet–blue region (420–450 nm). The emission intensity changes with the nature of capping agent. The PL intensity of ZnS–HPMC nanocomposites is found to be highest among the studied nanocomposites. The results clearly indicate that hydroxyl‐functionalized HPMC is much more effective at nucleating and stabilizing colloidal ZnS nanoparticles in aqueous suspensions compared with PVA and starch. Copyright © 2015 John Wiley & Sons, Ltd.     

A novel phosphorescence sensor for Co2+ ion based on Mn‐doped ZnS quantum dots

N‐acetyl‐l ‐cysteine‐capped Mn‐doped ZnS quantum dots (QDs) were prepared by hydrothermal methods. It could emit phosphorescence at 583 nm with the excitation wavelength at 315 nm. The phosphorescence intensity of QDs could be quenched dramatically by increasing the concentration of Co²⁺ ion. The novel phosphorescence sensor based on N‐acetyl‐l ‐cysteine‐capped QDs was developed for detecting Co²⁺ ion with a linear dynamic range of 1.25 × 10^–6–3.25 × 10^–5 m . The limit of detection and RSD were 6.0 × 10^–8 m and 2.3%, respectively. Interference experiments showed excellent selectivity over numerous cations such as alkali, alkaline earth and transitional metal ions. The possible quenching mechanism was also examined by phosphorescence decays. The proposed phosphorescence method was further applied to the trace determination of Co²⁺ ion in tap and pond water samples with recoveries of 97.75–103.32%. Copyright © 2013 John Wiley & Sons, Ltd.     

Luminescence study on Mn,Ni co‐doped zinc sulfide nanocrystals

Zinc sulfide (ZnS) doped with transition metal has been used as phosphor for various optoelectronic applications. In the present report, ZnS:Mn doped and ZnS:Mn,Ni co‐doped were prepared using chemical co‐precipitation method using polyvinyl pyrolidone as a surfactant. The structural studies were carried out using an X‐ray diffraction technique; optical studies have been performed using ultraviolet–visible light absorption and photoluminescence (PL) spectroscopy. The presences of functional groups were confirmed using Fourier transform infrared spectroscopy. The X‐ray diffraction study and Reitveld analysis confirms the formation of cubic phase with crystalline size 2–3 nm for undoped and doped ZnS nanoparticles. A novel and enhanced luminescence characteristic have been observed in PL spectra. The luminescence intensity of Mn,Ni co‐doped ZnS in the blue region is much higher of that of ZnS. The PL results indicate that the doping of Ni creates shallow trap states or luminescence centres in the forbidden energy gap, which quenches the Mn states emission. Concentration quenching has been observed in Mn‐doped ZnS nanoparticles. From CIE coordinates, it is seen that the yellow and blue light emission of ZnS:Mn,Ni co‐doped nanophosphor may be a promising candidate for display devices and phosphor converted light‐emitting diode 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.     

d‐penicillamine capped cadmium telluride quantum dots as a novel fluorometric sensor of copper(II)

d ‐penicillamine‐capped cadmium telluride quantum dots (DPA‐capped CdTe QDs) were synthesized as the new fluorescent semiconductor nanocrystal in aqueous solution. Fourier transmission infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, ultraviolet‐visible and photoluminescence spectroscopy were used for characterization of the QDs. Based on the quenching effect of Cu²⁺ ions on the fluorescence intensity of DPA‐capped CdTe QDs, a new fluorometric sensor for copper(II) detection was developed that showed good linearity over the concentration range 5 × 10^–9–3 × 10^–6 m with the detection limit 0.4 × 10^–9 m . Owing to the strong affinity of the DPA to copper(II), the sensor showed appropriate selectivity for copper(II) compared with conventional QDs. The DPA‐capped CdTe QDs was successfully applied for determination of Cu²⁺ concentration in river, well and tap waters with satisfactory results. Copyright © 2013 John Wiley & Sons, Ltd.     

Role of ERK1/2 in platelet lysate‐driven endothelial cell repair

Mechanisms of endothelial repair induced by a platelet lysate (PL) were studied on human (HuVEC, HMVEC‐c) and non‐human (PAOEC, bEnd5) endothelial cells. A first set of analyses on these cells showed that 20% (v/v) PL promotes scratch wound healing, with a maximum effect on HuVEC. Further analyses made on HuVEC showed that the ERK inhibitor PD98059 maximally inhibited the PL‐induced endothelial repair, followed in order of importance by the calcium chelator BAPTA‐AM, the PI3K inhibitor wortmannin and the p38 inhibitor SB203580. The PL exerted a chemotactic effect on HuVEC, which was abolished by all the above inhibitors, and induced a PD98059‐sensitive increase of cell proliferation rate. Confocal calcium imaging of fluo‐3‐loaded HuVEC showed that PL was able to induce cytosolic free Ca²⁺ oscillations, visible also in Ca²⁺‐free medium, suggesting an involvement of Ins3P‐dependent Ca²⁺ release. Western blot analysis on scratch wounded HuVEC showed that PL induced no activation of p38, a transient activation of AKT, and a sustained activation of ERK1/2. The complex of data indicates that, although different signalling pathways are involved in PL‐promoted endothelial repair, the process is chiefly under the control of ERK1/2. J. Cell. Biochem. 110: 783–793, 2010. © 2010 Wiley‐Liss, Inc.     

Eco‐friendly synthesis of gelatin‐capped bimetallic Au–Ag nanoparticles for chemiluminescence detection of anticancer raloxifene hydrochloride

This study described the utility of green analytical chemistry in the synthesis of gelatin‐capped silver, gold and bimetallic gold–silver nanoparticles (NPs). The preparation of nanoparticles was based on the reaction of silver nitrate or chlorauric acid with a 1.0 wt% aqueous gelatin solution at 50°C. The gelatin‐capped silver, gold and bimetallic NPs were characterized using transmission electron microscopy, UV–vis, X‐ray diffraction and Fourier transform infrared spectroscopy, and were used to enhance a sensitive sequential injection chemiluminescence luminol–potassium ferricyanide system for determination of the anticancer drug raloxifene hydrochloride. The developed method is eco‐friendly and sensitive for chemiluminescence detection of the selected drug in its bulk powder, pharmaceutical injections and biosamples. After optimizing the conditions, a linear relationship in the range of 1.0 × 10^–9 to 1.0 × 10^–1 mol/L was obtained with a limit of detection of 5.0 × 10^–10 mol/L and a limit of quantification of 1.0 × 10^‐9 mol/L. Statistical treatment and method validation were performed based on ICH guidelines. Copyright © 2016 John Wiley & Sons, Ltd.     

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.     

Effect of capping agent on the particle size of CdSe nanoparticles

CdSe nanoparticles were synthesized by green route and chemical route methods. In the green route method the samples were capped by starch and in the chemical route method the samples were capped by mercaptoacetic acid (MAA). The samples were characterized by powder X‐ ray diffraction (XRD) and transmission electron microscopy (TEM). Both the samples showed zinc blend structure. The optical absorption spectra and Fourier transform infrared (FTIR) spectra were also studied. A blue shift was seen in the absorption spectra as compared with the bulk as well as the sample capped by starch. TEM images showed agglomeration for the starch‐capped sample as compared with the MAA‐capped sample. The particle size for the sample capped by MAA was found to be less as compared with the starch‐capped sample. A blue shift in the photoluminescence (PL) spectra was also recorded for the samples prepared by the chemical route as compared with the sample prepared by the green route as well as the bulk. The PL peak shifted towards the red side and increase in the peak intensity occurred with the change in the excitation wavelength. Change in PL intensity was observed with different pH at 685 nm. Copyright © 2016 John Wiley & Sons, Ltd.     

ZnS quantum dots‐based fluorescence spectroscopic technique for the detection of quercetin

Water‐soluble ZnS quantum dots (QDs) modified by mercaptoacetic acid (MPA) were used to determinate quercetin in aqueous solutions by a fluorescence spectroscopic technique. The results showed that the fluorescence of the modified ZnS QDs could be quenched by quercetin effectively in physiological buffer solution. The optimum fluorescence intensity was found to be at incubation time 10 min, pH 7.0 and temperature 25°C. Under the optimal conditions, the detection limit of quercetin was 5.71 × 10^‐7 mol/L. Moreover, the quenching mechanism was discussed to be a static quenching procedure, which was proved by the quenching rate constant K_q (1.14 × 10¹³ L/mol/s). Copyright © 2013 John Wiley & Sons, Ltd. Copyright © 2013 John Wiley & Sons, Ltd.     

Study of fluorescence quenching of mercaptosuccinic acid‐capped CdS quantum dots in the presence of some heavy metal ions and its application to Hg(II) ion determination

In this study, CdS quantum dots (QDs) capped with mercaptosuccinic acid (MSA) were prepared in one step. The size, shape, component and spectral properties of MSA‐capped CdS QDs were characterized by transmission electron microscopy (TEM), photoluminescence (PL) and infrared (IR) spectrometry. The results showed that the prepared QDs with an average diameter of 6 nm have favorable fluorescence, which is greatly influenced by the pH of the environment. The interaction of some heavy metal ions including Ag⁺, Hg²⁺, Cu²⁺, Ni²⁺ and Co²⁺ with MSA‐capped CdS QDs was investigated in different buffering pH media. Based on the fluorescence quenching of the QDs in the presence of each of the metal ions, the feasibility of their determinations was examined according to the Stern–Volmer equation. The investigations showed that Hg(II) ions can be determined in the presence of many co‐existing metal ions at a buffering pH of 5. This method was satisfactorily applied to the measurement of Hg(II) ions in some environmental samples. Copyright © 2014 John Wiley & Sons, Ltd.     

Highly luminescent and biocompatible,l‐citrulline‐capped ZnS:Mn nanocrystals for rapid screening of metal accumulating Lysinibacillus fusiformis bacteria

Biocompatible and highly luminescent manganese doped zinc sulfide (ZnS:Mn) nanocrystals of average particle size 10 nm have been synthesized by capping with a novel amino acid ligand, l ‐citrulline. Though there are many reports on the bioimaging applications of nanostructured semiconductors, the present study focused on the detection of a special type of metal accumulating bacteria, Lysinibacillus fusiformis. This bacterium has significant applications in the disposal of metal components from industrial effluents. In this context, the detection of this bacterium is quite important and the present work demonstrates a novel technique for this bacterial detection. The synthesized nanocrystals were attached to Lysinibacillus fusiformis and characteristics of the bioconjugated system were studied. The blue shift observed in the ultraviolet‐visible absorption and photoluminescence spectra of the bioconjugated system, confirms conjugation of the Lysinibacillus fusiformis with l ‐citrulline‐capped ZnS:Mn. When the bioconjugated system (capped ZnS:Mn + bacteria) was observed using a fluorescent microscope under excitation wavelengths 365.4 nm (ultraviolet), 435.8 nm (blue) and 546.1 nm (green), fluorescence emissions were obtained in yellow, green and red regions respectively. The study of relative growth of Lysinibacillus fusiformis in the presence of l ‐citrulline‐capped ZnS:Mn proves biocompatible property of these nanocrystals and their tunable color properties under different excitation wavelengths make them ideal for biolabeling applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Comprehensive study of interaction between biocompatible PEG‐InP/ZnS QDs and bovine serum albumin

Polyethylene glycol (PEG) surface modified biocompatible InP/ZnS quantum dots (QDs) act as a potential alternative for conventional carcinogenic cadmium‐based quantum dots for in vivo and in vitro studies. Comprehensively, we studied the interaction between a model protein bovine serum albumin (BSA) and PEGylated toxic free InP/ZnS QDs using various spectroscopic tools such as absorption, fluorescence quenching, time resolved and synchronous fluorescence spectroscopic measurements. These studies principally show that tryptophan (Trp) residues of BSA have preferable binding affinity towards PEG‐InP/ZnS QDs surface and a blue shift in Trp fluorescence emission is a signature of conformational changes in its hydrophobic microenvironment. Photoluminescence (PL) intensity of Trp is quenched by ground state complex formation (static quenching) at room temperature. However, InP/ZnS@BSA conjugates become unstable with increasing temperature and PL intensity of Trp is quenched via dynamic quenching by PEG‐InP/ZnS QDs. Experimentally determined thermodynamic parameters for these conjugates have shown spontaneity, entropy driven and exothermic nature of bio‐conjugation. The calculated binding affinity (n ? 1, Hill coefficient) suggest that the affinity of InP/ZnS QDs for a BSA protein is not dependent on whether or not other BSA proteins are already bound to the QD surface. Energy transfer efficiency (E), Trp residue to InP/ZnS QDs distances and energy transfer rate (k_T) were all obtained from FÖrster resonance energy.