One‐pot synthesis and characterization CdTe:Zn2+ quantum dots and its molecular interaction with calf thymus DNA

Tremendous research efforts have been dedicated to fabricating high‐quality Zn‐doped CdTe quantum dots (QDs) for any potential biomedical applications. In particular, the correlation of issues regarding how QDs interact with DNA is of greatest importance. Herein, a pH‐responsive study of the interactions between CdTe:Zn²⁺ quantum dots with 4 different sizes and calf thymus DNA (ctDNA) was conducted using multispectroscopic techniques and electrochemical investigation. Fluorescence studies revealed that this interaction process is predominantly a static process and groove binding was the main binding mode for CdTe:Zn²⁺ QDs to ctDNA. The calculated negative values of enthalpy (?45.06 kJ mol^?1) and entropy (?133.62 J mol^?1 K^?1) with temperature changes indicated that the hydrogen bonds and van der Waals interactions played major roles in the reaction. Furthermore, circular dichroism spectroscopy and Fourier transform infrared spectrometry analyses indicate that the normal conformation of ctDNA is discombobulated by CdTe:Zn²⁺ QDs. In addition, the electrochemical behavior of the affinity of CdTe:Zn²⁺ QDs for ctDNA agreed well with the results obtained from fluorescence experiments. This study might be meaningful for understanding the molecular binding mechanism of QDs for DNA and provides a basis for QD‐labeled systems.     

Facile synthesis and photophysical characterization of luminescent CdTe quantum dots for Forster resonance energy transfer based immunosensing of staphylococcal enterotoxin B

Aqueous phase synthesis of CdTe quantum dots (QDs) with surface functionalization for bioconjugation remains the best approach for biosensing and bioimaging applications. We present a facile aqueous phase method to prepare CdTe QDs by adjusting precursor and ligand concentrations. CdTe QDs had photoluminescence quantum yield up to ≈33% with a narrow spectral distribution. The powder X‐ray diffraction profile elucidated characteristic broad peaks of zinc blende cubic CdTe nanoparticles with 2.5–3 nm average crystalline size having regular spherical morphology as revealed by transmission electron microscopy. Infra‐red spectroscopy confirmed disappearance of characteristic absorptions for –SH thiols inferring thiol coordinated CdTe nanoparticles. The effective molar concentration of 1 : 2.5 : 0.5 respectively for Cd²⁺/3‐mercaptopropionic acid/HTe^– at pH 9 ± 0.2 resulted in CdTe quantum dots of 2.2–3.06 nm having band gap in the range 2.74–2.26 eV respectively. Later, QD₅₂₃ and QD₆₀₁ were used for monitoring staphylococcal enterotoxin B (SEB; a bacterial superantigen responsible for food poisoning) using Forster resonance energy transfer based two QD fluorescence. QD₅₂₃ and QD₆₀₁ were bioconjugated to anti‐SEB IgY antibody and SEB respectively according to carbodiimide protocol. The mutual affinity between SEB and anti‐SEB antibody was relied upon to obtain efficient energy transfer between respective QDs resulting in fluorescence quenching of QD₅₂₃ and fluorescence enhancement of QD₆₀₁. Presence of SEB in the range 1–0.05 µg varied the rate of fluorescence quenching of QD₅₂₃, thereby demonstrating efficient use of QDs in the Forster resonance energy transfer based immunosensing method by engineering the QD size. Copyright © 2012 John Wiley & Sons, Ltd.     

Effects of N‐Acetyl‐L‐Cysteine‐Capped CdTe Quantum Dots on Bovine Serum Albumin and Bovine Hemoglobin: Isothermal Titration Calorimetry and Spectroscopic Investigations

The interactions of N‐acetyl‐L‐cysteine‐capped CdTe quantum dots (QDs) with bovine serum albumin (BSA) and bovine hemoglobin (BHb) were investigated by isothermal titration calorimetry (ITC), fluorescence, synchronous fluorescence, fluorescence lifetime, ultraviolet–visible absorption, and circular dichroism techniques. Fluorescence data of BSA–QDs and BHb–QDs revealed that the quenching was static in every system. While CdTe QDs changed the microenvironment of tryptophan in BHb, the microenvironment of BSA kept unchanged. Adding CdTe QDs affected the skeleton and secondary structure of the protein (BSA and BHb). The ITC results indicated that the interaction between the protein (BSA and BHb) and QDs‐612 was spontaneous and the predominant force was hydrophobic interaction. In addition, the binding constants were determined to be 1.19 × 10⁵ L mol^?1 (BSA–QDs) and 2.19 × 10⁵ L mol^?1 (BHb–QDs) at 298 K. From these results, we conclude that CdTe QDs have a larger impact on the structure of BHb than BSA.     

H2O2‐ and pH‐sensitive CdTe quantum dots as fluorescence probes for the detection of glucose

A novel fluorescence assay system for glucose was developed with thioglycollic acid (TGA)‐capped CdTe quantum dots (QDs) as probes. The luminescence quantum yield of the TGA‐capped CdTe QDs was highly sensitive to H₂O₂ and pH. In the presence of glucose oxidase, glucose is oxidized to yield, gluconic acid and H₂O₂. H₂O₂ and H⁺ (dissociated from gluconic acid) intensively quenched the fluorescence of QDs. The experimental results showed that the quenched fluorescence was proportional to the glucose concentration within the range of 0.01–5.0 mm under optimized experimental conditions. Compared with most of the existing methods, this newly developed system possesses many advantages, including simplicity, low cost, high flexibility, and good sensitivity. Furthermore, no complicated chemical modification of QDs and enzyme immobilization was needed in this system. Copyright © 2012 John Wiley & Sons, Ltd.     

A selective determination of copper ions in water samples based on the fluorescence quenching of thiol‐capped CdTe quantum dots

CdTe quantum dots (QDs) capped with different stabilizers, i.e. thioglycolic acid (TGA), 3‐mercaptopropionic acid (MPA) and glutathione (GSH) were investigated as fluorescent probes for the determination of Cu²⁺. The stabilizer was shown to play an important role in both the sensitivity and selectivity for the determination of Cu²⁺. TGA‐capped CdTe QDs showed the highest sensitivity, followed by the MPA and GSH‐capped CdTe QDs, respectively. The TGA‐ and MPA‐capped CdTe QDs were not selective for Cu²⁺ that was affected by Ag⁺. The GSH‐capped CdTe QDs were insensitive to Ag⁺ and were used to determine Cu²⁺ in water samples. Under optimal conditions, quenching of the fluorescence intensity (F₀/F) increased linearly with the concentration of Cu²⁺ over a range of 0.10–4.0 µg/mL and the detection limit was 0.06 µg/mL. The developed method was successfully applied to the determination of Cu²⁺ in water samples. Good recoveries of 93–104%, with a relative standard deviation of < 6% demonstrated that the developed simple method was accurate and reliable. The quenching mechanisms were also described. Copyright © 2015 John Wiley & Sons, Ltd.     

Core–shell structured CdTe/CdS@SiO2@CdTe@SiO2 composite fluorescent spheres: Synthesis and application for Cd2+ detection

Core–shell structured quantum dot (QD)–silica fluorescent nanoparticles have attracted a great deal of attention due to the excellent optical properties of QDs and the stability of silica. In this study, core–shell structured CdTe/CdS@SiO₂@CdTe@SiO₂ fluorescent nanospheres were synthesized based on the Stöber method using multistep silica encapsulation. The second silica layer on the CdTe QDs maintained the optical stability of nanospheres and decreased adverse influences on the probe during subsequent processing. Red‐emissive CdTe/CdS QDs (630 nm) were used as a built‐in reference signal and green‐emissive CdTe QDs (550 nm) were used as a responding probe. The fluorescence of CdTe QDs was greatly quenched by added S^2?, owing to a S^2?‐induced change in the CdTe QDs surface state in the shell. Upon addition of Cd²⁺ to the S^2?‐quenched CdTe/CdS@SiO₂@CdTe@SiO₂ system, the responding signal at 550 nm was dramatically restored, whereas the emission at 630 nm remained almost unchanged; this response could be used as a ratiometric ‘off–on’ fluorescent probe for the detection of Cd²⁺. The sensing mechanism was suggested to be: the newly formed CdS‐like cluster with a higher band gap facilitated exciton/hole recombination and effectively enhanced the fluorescence of the CdTe QDs. The proposed probe shows a highly sensitive and selective response to Cd²⁺ and has potential application in the detection of Cd²⁺ in environmental or biological samples.     

The behaviors of metal ions in the CdTe quantum dots–H2O2 chemiluminescence reaction and its sensing application

The behaviors of 15 kinds of metal ions in the thiol‐capped CdTe quantum dots (QDs)–H₂O₂ chemiluminescence (CL) reaction were investigated in detail. The results showed that Ag⁺, Cu²⁺ and Hg²⁺ could inhibit CdTe QDs and H₂O₂ CL reaction. A novel CL method for the selective determination of Ag⁺, Cu²⁺ and Hg²⁺ was developed, based on their inhibition of the reaction of CdTe QDs and H₂O₂. Under the optimal conditions, good linear relationships were realized between the CL intensity and the logarithm of concentrations of Ag⁺, Cu²⁺ and Hg²⁺. The linear ranges were from 2.0 × 10^?6 to 5.0 × 10^?8 mol L^?1 for Ag⁺, from 5.0 × 10^?6 to 7.0 × 10^?8 mol L^?1 for Cu²⁺ and from 2.0 × 10^?5 to 1.0 × 10^?7 mol L^?1 for Hg²⁺, respectively. The limits of detection (S/N = 3) were 3.0 × 10^?8, 4.0 × 10^?8 and 6.7 × 10^?8 mol L^?1 for Ag⁺, Cu²⁺ and Hg²⁺, respectively. A possible mechanism for the inhibition of CdTe QDs and H₂O₂ CL reaction was also discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

A sensitive fluorescent sensor based on the photoinduced electron transfer mechanism for cefixime and ctDNA

Cefixime is a third generation orally administered cephalosporin that is frequently used as a broad spectrum antibiotic against various gram‐negative and gram‐positive bacteria. In this study, a simple and sensitive fluorescent sensor for the determination of the cefixime and ctDNA was established based on the CdTe:Zn²⁺ quantum dots (QDs). The fluorescence of CdTe:Zn²⁺ QDs can be effectively quenched by cefixime in virtue of the surface binding of cefixime on CdTe:Zn²⁺ QDs and the subsequent photoinduced electron transfer process from CdTe:Zn²⁺ QDs to cefixime, in particular, the high sensitivity of QDs fluorescence emission to cefixime at the micromole per liter level, which render the cefixime‐CdTe:Zn²⁺ QDs system into fluorescence “OFF” status, then turn on in the presence of ctDNA. Furthermore, the Fourier transform infrared (FTIR) spectra of characteristic bands of C–N and N–H groups of cefixime endow evidence for the interaction of cefixime with CdTe:Zn²⁺ QDs. The relative electrochemical behavior of the affinity of CdTe:Zn²⁺ QDs for cefixime and ctDNA reveals the potential molecular binding mechanism.     

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.     

A highly selective and simple fluorescent sensor for mercury (II) ion detection based on cysteamine‐capped CdTe quantum dots synthesized by the reflux method

Cysteamine (CA)‐capped CdTe quantum dots (QDs) (CA–CdTe QDs) were prepared by the reflux method and utilized as an efficient nano‐sized fluorescent sensor to detect mercury (II) ions (Hg²⁺). Under optimum conditions, the fluorescence quenching effect of CA–CdTe QDs was linear at Hg²⁺ concentrations in the range of 6.0–450 nmol/L. The detection limit was calculated to be 4.0 nmol/L according to the 3σ IUPAC criteria. The influence of 10‐fold Pb²⁺, Cu²⁺ and Ag⁺ on the determination of Hg²⁺ was < 7% (superior to other reports based on crude QDs). Furthermore, the detection sensitivity and selectivity were much improved relative to a sensor based on the CA–CdTe QDs probe, which was prepared using a one‐pot synthetic method. This CA–CdTe QDs sensor system represents a new feasibility to improve the detection performance of a QDs sensor by changing the synthesis method. Copyright © 2014 John Wiley & Sons, Ltd.     

Graphene‐amplified electrogenerated chemiluminescence of CdTe quantum dots for H2O2 sensing

Electrogenerated chemiluminescence (ECL) of thiol‐capped CdTe quantum dots (QDs) in aqueous solution was greatly enhanced by PDDA‐protected graphene (P‐GR) film that were used for the sensitive detection of H₂O₂. When the potential was cycled between 0 and ?2.3 V, two ECL peaks were observed at ?1.1 (ECL‐1) and ?1.4 V (ECL‐2) in pH 11.0, 0.1 M phosphate buffer solution (PBS), respectively. The electron‐transfer reaction between individual electrochemically‐reduced CdTe nanocrystal species and oxidant coreactants (H₂O₂ or reduced dissolved oxygen) led to the production of ECL‐1. While mass nanocrystals packed densely in the film were reduced electrochemically, assembly of reduced nanocrystal species reacted with coreactants to produce an ECL‐2 signal. ECL‐1 showed higher sensitivity for the detection of H₂O₂ concentrations than that of ECL‐2. Further, P‐GR film not only enhanced ECL intensity of CdTe QDs but also decreased its onset potential. Thus, a novel CdTe QDs ECL sensor was developed for sensing H₂O₂. Light intensity was linearly proportional to the concentration of H₂O₂ between 1.0 × 10^?5 and 2.0 x 10^‐7 mol L^?1 with a detection limit of 9.8 x 10^?8 mol L^?1. The P‐GR thin‐film modified glassy carbon electrode (GCE) displayed acceptable reproducibility and long‐term stability. Copyright © 2012 John Wiley & Sons, Ltd.     

A simple and sensitive label‐free fluorescence sensing of heparin based on Cdte quantum dots

A rapid, simple and sensitive label‐free fluorescence method was developed for the determination of trace amounts of an important drug, heparin. This new method was based on water‐soluble glutathione‐capped CdTe quantum dots (CdTe QDs) as the luminescent probe. CdTe QDs were prepared according to the published protocol and the sizes of these nanoparticles were verified through transmission electron microscopy (TEM), X‐ray diffraction (XRD) and dynamic light scattering (DLS) with an average particle size of about 7 nm. The fluorescence intensity of glutathione‐capped CdTe QDs increased with increasing heparin concentration. These changes were followed as the analytical signal. Effective variables such as pH, QD concentration and incubation time were optimized. At the optimum conditions, with this optical method, heparin could be measured within the range 10.0–200.0 ng mL^?1 with a low limit of detection, 2.0 ng mL^?1. The constructed fluorescence sensor was also applied successfully for the determination of heparin in human serum. Copyright © 2015 John Wiley & Sons, Ltd.     

Enhanced electrochemiluminescence from reduced graphene oxide–CdTe quantum dots for highly selective determination of copper ion

An electrochemiluminescence (ECL) sensor based on reduced graphene oxide–CdTe quantum dots (RGO–CdTe QDs) composites for detecting copper ion (Cu²⁺) was proposed. The ECL behaviours of the RGO–CdTe QD modified electrode were investigated with H₂O₂ as the co‐reactant. Quantitative detection of Cu²⁺ was realized as Cu²⁺ could effectively quench the ECL signal of the RGO–CdTe QDs. A wide linear range of 1.00 × 10^?14 to 1.00 × 10^?4 M (R = 0.9953) was obtained under optimized conditions, and a detection limit (S/N = 3) was achieved of as low as 3.33 × 10^?15 M. The proposed sensor also exhibited good stability and selectivity for the detection of copper ions. Finally, the analytical application of the proposed sensor was also evaluated using river water.     

Flow‐injection chemiluminescence of the luminol–potassium periodate system enhanced by TGA–capped CdTe quantum dots for the determination of theophylline

The chemiluminescence (CL) behaviour of the luminol–potassium periodate system enhanced by CdTe quantum dots capped with thioglycolic acid (TGA–CdTe QDs) was studied using kinetic experiments, CL spectra, UV–vis absorption spectra and fluorescence spectra. The production of oxygen‐containing reactant intermediates (O₂^?? and OH^?) in the present CL system was verified by CL. The possible CL mechanism was discussed in detail. Furthermore, theophylline (THP) was determined based on its enhancement of the CL intensity of the CdTe QDs–luminol–potassium periodate system coupled with a flow‐injection technique. Under these optimized conditions, the linear range was found to be from 1.0 × 10^?8 to 1.0 × 10^?5 g/mL with a detection limit of 2.8 × 10^?9 g/mL (3σ). The recoveries for the determination of THP in tablets were from 98.2 to 99.6%.     

Highly luminescent hybrid SiO2‐coated CdTe quantum dots: synthesis and properties

Novel hybrid SiO₂‐coated CdTe quantum dots (QDs) were created using CdTe QDs coated with a hybrid SiO₂ shell containing Cd²⁺ ions and a sulfur source via a sol–gel process in aqueous solution. Aqueous CdTe QDs with tunable emitting color created through a reaction between cadmium chloride and sodium hydrogen telluride was used as cores for the preparation of hybrid SiO₂‐coated CdTe QDs. In our experiments we found that the surface state of the cores and preparation conditions that affect the formation of the hybrid SiO₂ shell also greatly affect photoluminescence of the hybrid SiO₂‐coated CdTe QDs. The generation of CdS‐like clusters in the vicinity of the CdTe QDs, caused the quantum size effect of the QDs to be greatly reduced, which changes photoluminescence properties of the hybrid QDs fundamentally. Namely, the novel hybrid SiO₂ shell played an important role in generating a series of specific optical properties. In addition, the novel hybrid SiO₂ shell can be created if no CdTe QD is added. In order to gain an insight into the inter structure of the hybrid shell, we characterized the hybrid SiO₂‐coated CdTe QDs using X‐ray diffraction analysis and discuss the formation mechanism of such a hybrid structure. This work is significant because the novel hybrid SiO₂‐coated CdTe QDs with its excellent properties can be used in many applications, such as biolabeling and optoelectronic devices. Copyright © 2013 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.     

A novel fluorescent assay for oxytetracycline hydrochloride based on fluorescence quenching of water‐soluble CdTe nanocrystals

A novel assay for oxytetracycline hydrochloride (OTC) based on fluorescence quenching was developed from the interaction between functionalized cadmium telluride quantum dots (CdTe QDs) and OTC. Optimum conditions for the detection of OTC were found after investigating all factors. Under optimum conditions, luminescence of CdTe nanocrystals (λ_ex = 365 nm, λ_em = 562 nm) was quenched by OTC in a concentration‐dependent manner best described by a modified Stern‐Volmer type equation. Good linearity was obtained with a regression coefficient of 0.9999 in the range of 1.34 ~ 13.4 x 10^‐5 mol/L and a limit of detection of 3.08 x 10^‐7 mol/L. In addition, the quenching mechanism was also established. The results imply that the close proximity of OTC‐CdTe was driven by electrostatic attraction and the resulting effective electron transfer from OTC to QDs could be responsible for fluorescence quenching of CdTe‐QDs. Copyright © 2012 John Wiley & Sons, Ltd.     

CdTe/ZnS quantum dots as fluorescent probes for ammonium determination

Novel CdTe/ZnS quantum dot (QD) probes based on the quenching effect were proposed for the simple, rapid, and specific determination of ammonium in aqueous solutions. The QDs were modified using 3‐mercaptopropionic acid, and the fluorescence responses of the CdTe/ZnS QD probes to ammonium were detected through regularity quenching. The quenching levels of the CdTe/ZnS QDs and ammonium concentration showed a good linear relationship between 4.0 × 10^?6 and 5.0 × 10^?4 mol/L; the detection limit was 3.0 × 10^?7 mol/L. Ammonium contents in synthetic explosion soil samples were measured to determine the practical applications of the QD probes and a probable quenching mechanism was described. Copyright © 2015 John Wiley & Sons, Ltd.     

Turn‐off–on chemiluminescence determination of cyanide

A flow injection chemiluminescence (FI–CL) method was developed for the determination of cyanide (CN⁻) based on the recovered CL signal by Cu²⁺ inhibiting a glutathione (GSH)‐capped CdTe quantum dot (QD) and hydrogen peroxide system. In an alkaline medium, strong CL signals were observed from the reaction of CdTe QDs and H₂O₂, and addition of Cu²⁺ could cause significant CL inhibition of the CdTe QDs–H₂O₂ system. In the presence of CN⁻, Cu²⁺ can be removed from the surface of CdTe QDs via the formation of particularly stable [Cu(CN)_n]^(n‐1)– species, and the CL signal of the CdTe QDs–H₂O₂ system was efficiently recovered. Thus, the CL signals of CdTe QDs–H₂O₂ system were turned off and turned on by the addition of Cu²⁺ and CN⁻, respectively. Further, the results showed that among the tested ions, only CN⁻ could recover the CL signal, which suggested that the CdTe QDs–H₂O₂–Cu²⁺ CL system had highly selectivity for CN⁻. Under optimum conditions, the CL intensity and the concentration of CN⁻ show a good linear relationship in the range 0.0–650.0 ng/mL (R² = 0.9996). The limit of detection for CN⁻ was 6.0 ng/mL (3σ). This method has been applied to detect CN⁻ in river water and industrial wastewater with satisfactory results. Copyright © 2014 John Wiley & Sons, Ltd.     

Photoluminescence properties of hybrid SiO2‐coated CdTe/CdSe quantum dots

Hybrid SiO₂‐coated CdTe/CdSe quantum dots (QDs) were prepared using CdTe/CdSe QDs prepared by hydrothermal synthesis. A CdSe interlayer made CdTe/CdSe cores with unique type II heterostructures. The hybrid SiO₂‐coated CdTe/CdSe QDs revealed excellent photoluminescence (PL) properties compared with hybrid SiO₂‐coated CdTe QDs. Because of the existence of spatial separations of carriers in the type II CdTe/CdSe core/shell QDs, the hybrid QDs had a relatively extended PL lifetime and high stability in phosphate‐buffered saline buffer solutions. This is ascribed to the unique components and stable surface state of hybrid SiO₂‐coated CdTe/CdSe QDs. During the stabilization test in phosphate‐buffered saline buffer solutions, both static and dynamic quenching occurred. The quenching mechanism of the hybrid QDs was not suited with the Stern–Volmer equation. However, the relative stable surface of CdTe/CdSe QDs resulted in lower degradation and relative high PL quantum yields compared with hybrid SiO₂‐coated CdTe QDs. As a result, hybrid SiO₂‐coated CdTe/CdSe QDs can be used in bioapplications. Copyright © 2013 John Wiley & Sons, Ltd.