Reversible Electrochemical Gelation of Metal Chalcogenide Quantum Dots.

The ability to dictate the assembly of quantum dots (QDs) is critical for their integration into solid-state electronic and optoelectronic devices. However, assembly methods that enable efficient electronic communication between QDs, facilitate access to the reactive surface, and retain the native quantum confinement characteristics of the QD are lacking. Here we introduce a universal and facile electrochemical gelation method for assembling metal chalcogenide QDs (as demonstrated for CdS, ZnS, and CdSe) into macroscale 3-D connected pore-matter nanoarchitectures that remain quantum confined and in which each QD is accessible to the ambient. Because of the redox-active nature of the bonding between QD building blocks in the gel network, the electrogelation process is reversible. We further demonstrate the application of this electrogelation method for a one-step fabrication of CdS gel gas sensors, producing devices with exceptional performance for NO2 gas sensing at room temperature, thereby enabling the development of low-cost, sensitive, and reliable devices for air quality monitoring.

Synthesis of pH Sensitive Dual Capped CdTe QDs: Their Optical Properties and Structural Morphology.

We herein report five different types of thiol dual capped cadmium tellurite quantum dots (CdTe QDs) namely glutathione-mercapto-propanoic acid (QD 1), glutathione-thiolglycolic acid (QD 2), L-cysteine-mercapto-propanoic acid (QD 3), L-cysteine- thiol-glycolic acid (QD 4) and mercapto-propanoic acid-thiol-glycolic (QD 5). Dual-capped CdTe QDs were prepared using a one pot synthetic method. Cadmium acetate and sodium tellurite were respectively used as cadmium and tellurium precursors. Photo-physical properties of the synthesized QDs were examined using UV-Vis and photoluminescence spectroscopy while structural characterization was performed by means of transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy. The influence of pH on QD characteristics (fluorescence intensity) was studied using phosphate and citrate buffers and continuous titration with HCl (0.1 N). UV-vis and photoluminescence spectra exhibited sharp absorption band edge with high intensities and improved colloidal stability. All the QDs were found to be in nano-size rang. TEM analysis revealed the presence of spherical nanoparticles while FTIR evidenced successful dual-capping of QDs. Upon pH changes, QDs 3 and 4 demonstrated more remarkable variations in fluorescence intensity than QDs 1 and 2. The pH-sensitivity of these QDs represents a promising feature for further development of potential theranostic nano-devices.

Three-Dimensional CdS@Carbon Fiber Networks: Innovative Synthesis and Application as a General Platform for Photoelectrochemical Bioanalysis.

This Letter reports a novel synthetic methodology for the fabrication of three-dimensional (3D) nanostructured CdS@carbon fiber (CF) networks and the validation of its feasibility for applications as a general platform for photoelectrochemical (PEC) bioanalysis. Specifically, 3D architectures are currently attracting increasing attention in various fields due to their intriguing properties, while CdS has been most widely utilized for PEC bioanalysis applications because of its narrow band gap, proper conduction band, and stable photocurrent generation. Using CdS as a representative material, this work realized the innovative synthesis of 3D CdS@CF networks via a simple solvothermal process. Exemplified by the sandwich immunoassay of fatty-acid-binding protein (FABP), the as-fabricated 3D CdS@CF networks exhibited superior properties, and the assay demonstrated good performance in terms of sensitivity and selectivity. This work features a novel fabrication of 3D CdS@CF networks that can serve as a general platform for PEC bioanalysis. The methodology reported here is expected to inspire new interest for the fabrication of other 3D nanostructured Cd-chalcogenide (S, Se, Te)@CF networks for wide applications in biomolecular detection and beyond.

Enzymatic Preparation of Plasmonic-Fluorescent Quantum Dot-Gold Hybrid Nanoprobes for Sensitive Detection of Glucose and Alkaline Phosphatase and Dual-Modality Cell Imaging.

Herein, we develop a route to prepare bifunctional plasmonic-fluorescent quantum dot-gold (QD-Au) hybrid nanoprobes by use of enzymatic reactions. Two bioenzymes, glucose oxidase (GOx) and alkaline phosphatase (ALP) were chosen for the enzymatic preparation of core-satellite or core-shell type CdSe/ZnS@Au hybrid nanostructures. The enzymatic products, H2O2 and l-ascorbic acid, of the two enzymes were exploited as mild reducing agents for controlled Au deposition on QD surfaces. The polymer multilayers by layer-by-layer assembly were used to adjust the separation between QD core and plasmonic Au, which can effectively reduce the quenching effect of the Au on QDs. The as-prepared QD@Au hybrid nanostructures are excellent dual-modality imaging nanoprobes, and can be used for fluorescence and dark-field scattering dual-imaging of MCF-7 cells. More importantly, the two enzymatic reaction systems can be explored for sensitive and selective detection of glucose and alkaline phosphatase, respectively, by monitoring the fluorescence spectra change of QD@Au hybrid nanoparticles, which is very useful for the glucose- and ALP-related disease diagnosis.

Ultrasensitive detection of glibenclamide based on its enhancing effect on the fluorescence emission of CdTe quantum dots.

Glibenclamide (GB), as a sulfonylurea-based medication is commonly prescribed for the treatment of type 2 diabetes. Due to its increasing consumption, there is a need to develop a simple, fast, and reliable detection method to follow its concentration in pharmaceutical and biological samples. Herein, a novel fluorometric method is developed for the sensitive measurement of GB. The method is based on the enhancing effect of GB on the fluorescence emission of mercaptopropionic acid (MPA) capped cadmium telluride quantum dots (CdTe QDs). QDs were synthesized in aqueous solution and were characterized by fluorescence spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Fluorescence intensity of QDs was enhanced by adding GB in a very low concentration. The effect of operative factors such as pH, buffer, contact time and concentration of CdTe QDs were investigated and in the optimized condition, a linear increase was achieved for the emission intensity of QDs by increasing GB concentration in the range 49-345 ng mL-1 , with a detection limit of 17.84 ng mL-1 . The offered method has an acceptable precision (relative standard deviations were < 2.8%) and was satisfactorily applied for the determination of GB in pharmaceutical products and human urine samples.

Synthesis and characterization of cadmium selenide quantum dots doped by europium and investigation of their chemiluminescence properties and antibacterial activities.

Nanoparticles of cadmium selenide (CdSe) doped with europium, were synthesized as stabilizing agents using thioglycolic acid ligand. This method is based on the enhancing effect of CdSe quantum dots (QDs) doped with europium on chemiluminescence (CL) emission. This emission was generated by mixing CdSe QDs with manganese (II), iron (II) and chrome (II) sulfates as catalysts in the presence of hydrogen peroxide (H2 O2 ). The structural characteristics and morphology of these nanoparticles were investigated by scanning electron microscopy, Fourier transform infrared spectroscopy, ultraviolet-visible absorption spectroscopy, X-ray pattern and dynamic light scattering methods. The CdSe QDs doped with europium were used as the sensitizer in a luminol-hydrogen peroxide CL system. The sensitized CdSe QDs were analyzed for antibacterial activity against Gram-positive or Gram-negative bacteria. The results showed that the CdSe QDs are effective against all the studied bacteria, effectiveness was especially higher for Bacillus subtilis.

Preparation of Microkernel-Based Mesoporous (SiO2-CdTe-SiO2)@SiO2 Fluorescent Nanoparticles for Imaging Screening and Enrichment of Heat Shock Protein 90 Inhibitors from Tripterygium Wilfordii.

The currently utilized ligand fishing for bioactive molecular screening from complex matrixes cannot perform imaging screening. Here, we developed a new solid-phase ligand fishing coupled with an in situ imaging protocol for the specific enrichment and identification of heat shock protein 90 (Hsp 90) inhibitors from Tripterygium wilfordii, utilizing a multiple-layer and microkernel-based mesoporous nanostructure composed of a protective silica coating CdTe quantum dot (QD) core and a mesoporous silica shell, i.e., microkernel-based mesoporous (SiO2-CdTe-SiO2)@SiO2 fluorescent nanoparticles (MMFNPs) as extracting carries and fluorescent probes. The prepared MMFNPs showed a highly uniform spherical morphology, retention of fluorescence emission, and great chemical stability. The fished ligands by Hsp 90α-MMFNPs were evaluated via the preliminary bioactivity based on real-time cellular morphology imaging by confocal laser scanning microscopy (CLSM) and then identified by mass spectrometry (MS). Celastrol was successfully isolated as an Hsp 90 inhibitor, and two other specific components screened by Hsp 90α-MMFNPs, i.e., demecolcine and wilforine, were preliminarily identified as potential Hsp 90 inhibitors through the verification of strong affinity to Hsp 90 and antitumor bioactivity. The approach based on the MMFNPs provides a strong platform for imaging screening and discovery of plant-derived biologically active molecules with high efficiency and selectivity.

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.

Chiral ligand-induced photoluminescence intermittence difference of CdTe quantum dots.

Semiconductor quantum dots (QDs) are a new nano-material, and their unique optical properties have become a focal point of research in both academia and industry. In this study, we studied photoluminescence (PL) intermittence (or 'blinking') behaviors of individual QDs prepared with different chiral ligands by using single molecule microscopy and single molecule fluorescence correlation spectroscopy (FCS). We found that the chirality of N-isobutyryl-d/l-cysteine (D/L-NIC) as surface stabilizers significantly influences PL blinking behaviors of cadmium telluride (CdTe) QDs synthesized in aqueous solution. The 'on time' distribution and the power-law exponent analyses show that the D-NIC more efficiently suppresses the blinking of QDs over L-NIC. Ensemble spectroscopies verfied that the remarkably-different blinking behaviors of QDs induced by ligand chirality were attributed to the different number of chiral ligands bound in the surface of QDs.

Synthesis, characterization and optical property investigation of CdS nanoparticles.

Microwave-assisted routes have attracted much attention for nanoparticle synthesis because of minimal solvent use and rapid, high efficiency and controlled morphology. Cadmium sulphide (CdS) nanoparticles form the line between bulk and molecular states of materials and show variation in their physical and chemical properties. Cadmium sulphate and thiourea were used as precursors during this synthesis. These are included in the category of practical semiconductor metal sulphides, which are extensively used as catalysts and optical materials. X-ray diffraction (XRD) patterns confirmed that CdO nanoparticles are crystalline and have a hexagonal phase with crystal sizes that agree with transmission electron microscopy (TEM) data. UV-visible spectroscopy and photoluminescence (PL) spectroscopy were used to evaluate optical properties using band gap energy measurements.

CdSe and CdSe/CdS core-shell QDs: New approach for synthesis, investigating optical properties and application in pollutant degradation.

In this work, CdSe quantum dots (QDs) were synthesized by a simple and rapid microwave activated approach using CdSO4 , Na2 SeO3 as precursors and thioglycolic acid (TGA) as capping agent molecule. A novel photochemical approach was introduced for the growth of CdS QDs and this approach was used to grow a CdS shell around CdSe cores for the formation of a CdSe/CdS core-shell structure. The core-shells were structurally verified using X-ray diffraction, transmission electron microscopy and FTIR (Fourier-transform infrared (FTIR)) spectroscopy. The optical properties of the samples were examined by means of UV-Vis and photoluminescence (PL) spectroscopy. It was found that CdS QDs emit a broad band white luminescence between 400 to 700 nm with a peak located at about 510 nm. CdSe QDs emission contained a broad band resulting from trap states between 450 to 800 nm with a peak located at 600 nm. After CdS shell growth, trap states emission was considerably quenched and a near band edge emission was appeared about 480 nm. Optical studies revealed that the core-shell QDs possess strong ultraviolet (UV) - visible light photocatalytic activity. CdSe/CdS core-shell QDs, showed an enhancement in photodegradation of Methyl orange (MO) compared with CdSe QDs.

Hydride Generation for Headspace Solid-Phase Extraction with CdTe Quantum Dots Immobilized on Paper for Sensitive Visual Detection of Selenium.

A low-cost, simple, and highly selective analytical method was developed for sensitive visual detection of selenium in human urine both outdoors and at home, by coupling hydride generation with headspace solid-phase extraction using quantum dots (QDs) immobilized on paper. The visible fluorescence from the CdTe QDs immobilized on paper was quenched by H2Se from hydride generation reaction and headspace solid-phase extraction. The potential mechanism was investigated by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) as well as Density Functional Theory (DFT). Potential interferences from coexisting ions, particularly Ag(+), Cu(2+), and Zn(2+), were eliminated. The selectivity was significantly increased because the selenium hydride was effectively separated from sample matrices by hydride generation. Moreover, due to the high sampling efficiency of hydride generation and headspace solid phase extraction, the sensitivity and the limit of detection (LOD) were significantly improved compared to conventional methods. A LOD of 0.1 µg L(-1) and a relative standard deviation (RSD, n = 7) of 2.4% at a concentration of 20 µg L(-1) were obtained when using a commercial spectrofluorometer as the detector. Furthermore, a visual assay based on the proposed method was developed for the detection of Se, 5 µg L(-1) of selenium in urine can be discriminated from the blank solution with the naked eye. The proposed method was validated by analysis of certified reference materials and human urine samples with satisfactory results.

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.

Sensitive determination of enoxacin in pharmaceutical formulations by its quench effect on the fluorescence of glutathione-capped CdTe quantum dots.

A sensitive and simple method for the determination of enoxacin (ENX) was developed based on the fluorescence quenching effect of ENX for glutathione (GSH)-capped CdTe quantum dots (QDs). Under optimum conditions, a good linear relationship was obtained from 4.333 × 10(-9) mol⋅L(-1) to 1.4 × 10(-5) mol⋅L(-1) with a correlation coefficient (R) of 0.9987, and the detection limit (3σ/K) was 1.313 × 10(-9) mol⋅L(-1). The corresponding mechanism has been proposed on the basis of electron transfer supported by ultraviolet-visible (UV) light absorption, fluorescence spectroscopy, and the measurement of fluorescence lifetime. The method has been applied to the determination of ENX in pharmaceutical formulations (enoxacin gluconate injections and commercial tablets) with satisfactory results. The proposed method manifested several advantages such as high sensitivity, short analysis time, low cost and ease of operation.

Constructing a MoS2 QDs/CdS Core/Shell Flowerlike Nanosphere Hierarchical Heterostructure for the Enhanced Stability and Photocatalytic Activity.

MoS2 quantum dots (QDs)/CdS core/shell nanospheres with a hierarchical heterostructure have been prepared by a simple microwave hydrothermal method. The as-prepared samples are characterized by XRD, TEM, SEM, UV-VIS diffuse reflectance spectra (DRS) and N2-sorption in detail. The photocatalytic activities of the samples are evaluated by water splitting into hydrogen. Results show that the as-prepared MoS2 QDs/CdS core/shell nanospheres with a diameter of about 300 nm are composed of the shell of CdS nanorods and the core of MoS2 QDs. For the photocatalytic reaction, the samples exhibit a high stability of the photocatalytic activity and a much higher hydrogen evolution rate than the pure CdS, the composite prepared by a physical mixture, and the Pt-loaded CdS sample. In addition, the stability of CdS has also been greatly enhanced. The effect of the reaction time on the formations of nanospheres, the photoelectric properties and the photocatalytic activities of the samples has been investigated. Finally, a possible photocatalytic reaction process has also been proposed.

Photocatalytic Activities of Copper Doped Cadmium Sulfide Microspheres Prepared by a Facile Ultrasonic Spray-Pyrolysis Method.

Ultrasonic spray pyrolysis is a superior method for preparing and synthesizing spherical particles of metal oxide or sulfide semiconductors. Cadmium sulfide (CdS) photocatalysts with different sizes and doped-CdS with different dopants and doping levels have been synthesized to study their properties of photocatalytic hydrogen production from water. The CdS photocatalysts were characterized with scanning electron microscopy (SEM), X-ray fluorescence-spectrometry (XRF), UV-Vis absorption spectra and X-ray diffraction (XRD) to study their morphological and optical properties. The sizes of the prepared CdS particles were found to be proportional to the concentration of the metal nitrates in the solution. The CdS photocatalyst with smaller size showed a better photocatalytic activity. In addition, Cu doped CdS were also deposited and their photocatalytic activities were also investigated. Decreased bandgaps of CdS synthesized with this method were found and could be due to high density surface defects originated from Cd vacancies. Incorporating the Cu elements increased the bandgap by taking the position of Cd vacancies and reducing the surface defect states. The optimal Cu-doped level was found to be 0.5 mol % toward hydrogen evolution from aqueous media in the presence of sacrificial electron donors (Na2S and Na2SO3) at a pH of 13.2. This study demonstrated that ultrasonic spray pyrolysis is a feasible approach for large-scale photocatalyst synthesis and corresponding doping modification.

Highly Sensitive and Selective Photoelectrochemical Biosensor for Hg(2+) Detection Based on Dual Signal Amplification by Exciton Energy Transfer Coupled with Sensitization Effect.

A highly sensitive and selective photoelectrochemical (PEC) biosensor for Hg(2+) detection was developed on the basis of the synergistic effect of exciton energy transfer (EET) between CdS quantum dots (QDs) and Au nanoparticles (NPs) coupled with sensitization of rhodamine 123 (Rh123) for signal amplification. First, the TiO2/CdS hybrid structure obtained by depositing CdS QDs on TiO2 film was employed as a matrix for immobilizing probe DNA (pDNA). Next, Rh123 was introduced into the pDNA terminal, and then Au NP labeled target DNA (Au-tDNA) was hybridized with pDNA to form a rod-like double helix structure. The detection of Hg(2+) was based on a conformational change of the pDNA after incubating with Hg(2+). In the absence of Hg(2+), Rh123 was located away from the electrode surface due to the DNA hybridization, leading to inhibition of the sensitization effect, and meanwhile, the occurrence of EET between CdS QDs and Au NPs resulted in a photocurrent decrease. However, after incubating with Hg(2+), the rod-like double helix was disrupted, and the energy transfer was broken. In this case, the photocurrent recovered, and meanwhile, the folded pDNA made the labeled Rh123 move closer to the electrode surface, leading to the formation of the sensitization structure, which evidently increased the photocurrent intensity. The sensitivity of the biosensor for Hg(2+) detection was greatly enhanced for the dual signal amplification strategy. The linear range was 10 fM to 200 nM, with a detection limit of 3.3 fM. This biosensor provides a promising new platform for detecting various heavy metal ions at ultralow levels.

A steady-state and time-resolved photophysical study of CdTe quantum dots in water.

The exciton generation and recombination dynamics in semiconductor nanocrystals are very sensitive to small variations in dimensions, shape and surface capping. In the present work CdTe quantum dots are synthesized in water using 3-mercaptopropionic acid and 1-thioglycerol as stabilizers. Nanocrystals with an average dimension of 4.0 ± 1.0 and 3.7 ± 0.9 nm were obtained, when 3-mercaptopropionic acid or 1-thioglycerol, respectively, was used as a capping agent. The steady-state characterization shows that the two types of colloids have different luminescence behavior. In order to investigate the electronic structure and the dynamics of the exciton state, a combined study in the time domain has been carried out by using fluorescence time-correlated single photon counting and femtosecond transient absorption techniques. The electron-hole radiative recombination follows the non-exponential decay law for both colloids, which results in different average decay time values (of the order of tens of nanoseconds) for the two samples. The data demonstrate that the process is slower for 1-thioglycerol-stabilized colloids. The ultrafast transient absorption measurements are performed at two different excitation wavelengths (at the band gap and at higher energies). The spectra are dominated in both types of samples by the negative band-gap bleaching signals although transient positive absorption bands due to the electrons in the conduction band are observable. The analysis of the signals is affected by the different interactions with the defect states, due to ligand capping capacities. In particular, the data indicate that in 1-thioglycerol-stabilized colloids the non-radiative recombination processes are kinetically more competitive than the radiative recombination. Therefore the comparison of the data obtained from the two samples is interpreted in terms of the effects of the capping agents on the electronic relaxation of the colloids.

Selective anion exchange and tunable luminescent behaviors of metal-organic framework based supramolecular isomers.

Owing to the conformational (cis or trans) flexibility of a N-donor ligand, the combinations of the same and Cd(ClO4)2 under variable solvent templates afforded two supramolecular isomers based on two-dimensional metal-organic frameworks. Both compounds contain weakly coordinating ClO4(-) anions attached to the metal centers. Both frameworks showed facile anion exchange behaviors with various kinds of foreign anions. Moreover, both frameworks showed anion-driven structural dynamism and exhibited the preferential uptake of strongly coordinating anions over others. Anion-regulated modulation in luminescent behaviors was also observed in both cases.

Fluorescence Determination of Warfarin Using TGA-capped CdTe Quantum Dots in Human Plasma Samples.

In this study, some effort has been performed to provide low temperature, less time consuming and facile routes for the synthesis of CdTe quantum dots using ultrasound and water soluble capping agent thioglycolic acid. TGA-capped CdTe quantum dots were characterized through x-ray diffraction, transmission electron microscopy, Fourier transform infrared, ultraviolet-visible and fluorescence spectroscopy. The prepared quantum dots were used for warfarin determination based on the quenching of the fluorescence intensity in aqueous solution. Under the optimized conditions, the linear range of quantum dots fluorescence intensity versus the concentration of warfarin was 0.1-160.0 µM, with the correlation coefficient of 0.9996 and a limit of detection of 77.5 nM. There was no interference to coexisting foreign substances. The selectivity of the sensor was also tested and the results show that the developed method possesses a high selectivity for warfarin.