Facile preparation of cds quantum dots using hyperbranched poly(amidoamine)s with hydrophobic end‐groups as nanoreactors

Hyperbranched poly(amidoamine)s with methyl ester terminals (HPAMAM) were synthesized by one‐pot approach and subsequently used as nanoreactors to prepare CdS quantum dots (QDs). HPAMAM could bind Cd²⁺ through their internal amines, while the external methyl ester groups prevented the aggregation of polymers. After reaction with S^2?, CdS QDs sequestered within individual hyperbranched polymers were obtained. The resulting CdS/HPAMAM nanocomposites were characterized by dynamic light scattering, transmission electron microscopy, ultraviolet‐visible spectroscopy, photoluminescence spectroscopy, and Fourier transform infrared spectroscopy, confirming the formation of CdS QDs with small particle size and narrow size‐distribution. Furthermore, the effects of Cd²⁺/S^2? ratio and aging time on the photoluminescence of CdS QDs were also investigated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Facile preparation of highly luminescent CdTe quantum dots within hyperbranched poly(amidoamine)s and their application in bio-imaging

A new strategy for facile preparation of highly luminescent CdTe quantum dots (QDs) within amine-terminated hyperbranched poly(amidoamine)s (HPAMAM) was proposed in this paper. CdTe precursors were first prepared by adding NaHTe to aqueous Cd²⁺ chelated by 3-mercaptopropionic sodium (MPA-Na), and then HPAMAM was introduced to stabilize the CdTe precursors. After microwave irradiation, highly fluorescent and stable CdTe QDs stabilized by MPA-Na and HPAMAM were obtained. The CdTe QDs showed a high quantum yield (QY) up to 58%. By preparing CdTe QDs within HPAMAM, the biocompatibility properties of HPAMAM and the optical, electrical properties of CdTe QDs can be combined, endowing the CdTe QDs with biocompatibility. The resulting CdTe QDs can be directly used in biomedical fields, and their potential application in bio-imaging was investigated.     

In situ preparation of fluorescent CdTe quantum dots with small thiols and hyperbranched polymers as co-stabilizers

A new strategy for in situ preparation of highly fluorescent CdTe quantum dots (QDs) with 3-mercaptopropionic acid (MPA) and hyperbranched poly(amidoamine)s (HPAMAM) as co-stabilizers was proposed in this paper. MPA and HPAMAM were added in turn to coordinate Cd²⁺. After adding NaHTe and further microwave irradiation, fluorescent CdTe QDs stabilized by MPA and HPAMAM were obtained. Such a strategy avoids the aftertreatment of thiol-stabilized QDs in their bioapplication and provides an opportunity for direct biomedical use of QDs due to the existence of biocompatible HPAMAM. The resulting CdTe QDs combine the mechanical, biocompatibility properties of HPAMAM and the optical, electrical properties of CdTe QDs together.     

Suspension polymerization stabilized by triblock copolymer with CdS nanoparticles

In this paper, a new method to prepare polymer colloid particles stabilized by triblock copolymer with CdS nanoparticles was described. Poly(ethylene glycol-block-styrene-block-2-(dimethylamino) ethyl methacrylate) (PEG-b-PS-b-PDMAEMA) triblock copolymer was synthesized by sequential ATRP method. Micelles with CdS nanoparticles in the corona were prepared by “in situ” reaction of hydrogen sulfide with cadmium ion clusters in the corona of the micelles. The size of the CdS nanoparticles is affected by molar ratio of DMAEMA to cadmium ions and polymer concentration in the solution. When introduced into o/w emulsion the micelles reassemble on the surface of styrene oil droplets. PS colloid particles stabilized by triblock copolymer with CdS nanoparticles were achieved by suspension polymerization. TEM image indicates that CdS nanoparticles locate at the surface of the PS colloid particles.     

Luminescence Enhancement of CdS Quantum Dots in Glass by Ag+ Ion Exchange

Luminescence of CdS quantum dots (QDs) enhanced by the induction of Ag nanoparticles (NPs) in glasses was investigated. Ag⁺ ions diffused into glasses containing CdS QDs by ion exchange, then formed Ag NPs after subsequent heat treatment. Luminescence intensity of CdS QDs increased approximately three times when the ion‐exchange duration was 1 min, but was severely quenched when the duration was extended to 30 min. Increasing the amount of Ag⁺ ions increased the number of Ag NPs and decreased the average distance between Ag NPs and CdS QDs. This decrease in the average distance induced the changes of luminescence intensity.     

Recovery of cadmium from a zinc hydrometallurgical leachate using reactive emulsion liquid membrane technology

A new emulsion liquid membrane process using 3,5‐diisopropylsalicylic acid (DIPSA) and triisobutylphosphine sulfide (TIBPS) as carriers, and ammonium sulfide (NH₄)₂S as precipitant is described. The reactive nature of sulfide ions with extracted cadmium ions in the internal aqueous phase significantly increases cadmium recovery and minimizes zinc impurities. The new process is applied to the enrichment of a low concentration of cadmium ions from a solution containing a high concentration of zinc ions. Under optimum operating conditions, a single stage process produced a cadmium recovery of 98% at a cadmium sulfide content of 99.6%. The results are encouraging for potential applications in zinc hydrometallurgy for recovery of cadmium from sulfuric acid leaching solution of zinc ores. Copyright © 2004 Society of Chemical Industry     

Surface modification and fabrication of white-light-emitting Tm3+/CdS quantum dots co-doped glass fibers

Due to the widely tunable band gap and broadband excitation, CdS quantum dots (QDs) show great promise for yellow-light luminescence center in white-light-emitting devices. The light intensity of the CdS QD-doped glass was enhanced by doping the Tm³⁺ ions due to the higher absorption rate. The influence of Tm³⁺ ions on the surface structure of CdS QDs was enormous according to the first-principles calculations. Doping Tm³⁺ ions change the surface state of CdS QDs, which will fix the QDs emission peaks and enhance the luminescence of CdS QDs at a lower heat-treatment temperature. White-light emission was obtained by tuning the relative concentration between Tm³⁺/CdS QDs. However, there is a fundamental challenge to fabricate QD-doped glass fibers by rod-in-tube method since uncontrollable QDs crystallization is hard to avoid. Herein, a white-light-emitting borosilicate glass fiber was fabricated by the “melt-in-tube” method using a special designed Tm³⁺/CdS QDs co-doped borosilicate glass with low-melting temperature as fiber core. After heat treatment, ideal white-light emission was observed from the fiber under excitation at single wavelength (359 nm). This finding indicates that Tm³⁺/CdS QDs co-doped glass fiber with white-light-emitting devices has potential application as gain medium of white-light-emitting sources and fiber lasers.     

A highly selective electrochemical sensor for l‐tryptophan based on a screen‐printed carbon electrode modified with poly‐p‐phenylenediamine and CdS quantum dots

A new highly selective electrochemical sensor for the determination of l ‐tryptophan was proposed by modifying the surface of screen‐printed carbon electrodes (SPCEs). The surface of SPCE was firstly modified by electropolymerization of p‐phenylenediamine (PPD). The polymer film was then covalently linked with cysteamine capped cadmium sulfide quantum dots (Cys‐CdS QDs) by using glutaraldehyde (GA) as a cross‐linker resulted in an organic–inorganic hybrid composite film (QDs/GA/PPD/SPCE). The modified electrode was applied as a working electrode for detecting various amino acids. It was found that the modified electrode gave an electrochemical response selectively to l ‐tryptophan over other amino acids. The experimental parameters, including pH of solution, buffer types, electropolymerization cycles, scan rate, and accumulation time, were studied and optimized. The proposed sensor can be used to detect l ‐tryptophan with a low detection limit of 14.74 µmol L^?1 with good precision and the relative standard deviation less than 3.7%. The modified electrode was used to detect l ‐tryptophan in beverage samples and gave satisfactory recoveries from 91.9 to 104.9%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40356.     

Transitions of domain ordering and domain size in a spherical-forming polystyrene-block-poly(ethylene oxide) copolymer and its composites with colloidal cadmium sulfide quantum dots

With specific annealing schemes applied to a neat polystyrene-block-poly(ethylene oxide) (SE) and its composites with cadmium sulfide quantum dots (CdS QD), we have observed microdomain structures and phase transitions in the system using temperature-resolved small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Both TEM images and SAXS results show clearly that incorporation of surfactant-tethered CdS QD preferentially into PEO blocks leads to increases in thermal stabilities of both bcc-packed lattice (referred as long-range order) and microdomains themselves in the sphere-forming SE/CdS composites. The bcc-packed lattice in the SE/CdS composites sustains better than that in the neat SE, during a temperature elevation to ∼160 °C, at which the bcc-packed SE/CdS spheres start to transform into micelles with a short-range liquid-like order. Quantitative model analysis shows that the PEO/CdS micelles can retain their size in the SE/CdS composites up to 200 °C, whereas the PEO micelles shrink after the softening of the PS matrix around 100 °C, and disassociate largely into the PS matrix of the neat SE at 160 °C.     

Phase Controlled Monodispersed CdS Nanocrystals Synthesized in Polymer Solution Using Microwave Irradiation

Cadmium sulfide (CdS) nanocrystals were synthesized in aqueous solution of polyvinyl pyrrolidone (PVP) via the simple and rapid microwave irradiation method. It is revealed that sulfur source is a key factor in controlling the phase formation of the resulting nanocrystals. The hexagonal and cubic structure of CdS nanocrystals could be obtained with varying sulfur sources of thioacetamide and sodium sulphide respectively. The interaction mechanism of PVP with precursor ions of cadmium and sulfur sources in the preparation process was proposed. It is found that PVP compounded the CdS nanoparticles and protected them from agglomerating. With increasing of PVP concentration, the average particle size of CdS nanocrystals increased and subsequently their optical band gap decreased. At the appropriate dosage of PVP, well isolated nanoparticles with relatively narrow size distribution were obtained for both sulfur sources. Moreover the stability of CdS nanoparticles enhanced after coating with polymer.     

Structure and Properties of CdS/Regenerated Cellulose Nanocomposites

Summary: Novel inorganic‐organic hybrid materials composed of cadmium sulfide (CdS) semiconducting nanocrystals and regenerated cellulose (RC) were prepared by using in situ synthesizing method. Cellulose was dissolved in a 6 wt.‐% NaOH/4 wt.‐% urea/thiourea aqueous solution at low temperature followed by addition of cadmium chloride (CdCl₂), resulting that the CdS nanocrystals were successfully grown in situ in the cellulose solution. Nanocomposite films containing homogeneous CdS nanoparticles were obtained by casting the resulting solution. Their structure and optical properties were characterized by X‐ray photoelectron spectroscopy, wide‐angle X‐ray diffraction, thermogravimetry analysis, dynamic mechanical analysis, atomic force microscopy, transmittance electronic microscope, UV‐vis spectroscopy, and photoluminescence spectroscopy. The experimental results confirmed that the CdS nanocrystalline existed in the composite films, and cellulose matrix provided a confined medium for CdS particle growth in uniform size. The CdS/RC composites showed narrow emission in photoluminescence spectra, and their optical absorbance in the UV range was higher than that of the cellulose film without CdS. This work provided a simple method to prepare cellulose functional materials in NaOH/urea aqueous solution.

Photoluminescence of CdS/RC nanocomposites and TEM image of CdS nanocrystals dispersed in RC matrix.     

Investigation of multilayered quantum dot-sensitized solar cells with different Zn chalcogenide passivation layers

In the case of cadmium sulfide (CdS) and cadmium selenide (CdSe)-based quantum dot-sensitized solar cells (QDSSCs), the addition of a zinc sulfide (ZnS) passivation layer improves the solar cell performance. In this study, multilayered QDSSCs were fabricated using CdS and CdSe quantum dots prepared by successive ionic layer adsorption and reaction (SILAR) method. The optimized QDSSCs were used to study the passivation effect of zinc chalcogenide layers: ZnS, zinc selenide (ZnSe), and zinc telluride (ZnTe). The best performing solar cell prepared from four SILAR cycles of CdS followed by six SILAR cycles of CdSe were used for subsequent deposition of Zn chalcogenide layers. It was observed that capping with ZnSe or ZnTe layer on the multilayered Cd chalcogenide QDs did not improve the solar cell performance. Only the addition of ZnS layer contributed to the better performance of the solar cell. The efficiency obtained in the optimized multilayered CdS/CdSe QDSSC with ZnS layer was 1.37 %, while the QDSSC with ZnSe or ZnTe capping showed lower performance. The behavior of the solar cells is explained with electrochemical impedance spectroscopy study.     

Synthesis and elastomer behavior of a novel polymer electrolyte of acrylic ester–salt copolymer

This paper studied the synthesis of a novel elastomeric copolymer electrolyte in an aqueous phase. The monomer, sodium allyl sulfonate (SAS), was dissolved in continuous aqueous phase and the second monomer, methyl acrylate (MA), was supplied from MA micelles as dispersed phase. The copolymerization of the two monomers took place in continuous aqueous phase. Confirmed by FTIR and ¹H‐NMR, a binary copolymer electrolyte of MA and SAS, poly(MA‐co‐SAS), was obtained. The glass transition temperature of the copolymer was indicated as 20.4°C by DSC thermogram, thus, it behaves an elastomer in normal ambient temperature. The mechanical properties of the composite films consisting of both poly(MA‐co‐SAS) and Cu²⁺ ions or reduced copper were affected by the content of ions and reduced copper. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2796–2802, 2006     

Self-assembled CdS quantum dots-sensitized TiO2 nanospheroidal solar cells: Structural and charge transport analysis

A nanospheroidal TiO₂ mesoporous layer combined with cadmium sulfide (CdS) quantum dots (QDs) as a sensitizer was firstly utilized for solar cell applications, resulting in an efficiency of 1.2% at a 1 sun condition. CdS quantum dots (18 nm) were attached to the TiO₂ nanospheroidal electrode by using a chemical bath deposition technique. The influence of surface treatment using dimethyl formamide on the interconnectivity of the TiO₂ nanospheroidal electrodes was investigated. The charge transport of TiO₂/CdS QDs/electrolyte sandwich-type cells was characterized by electrochemical impedance spectroscopy and the device performance was compared with conventional nanospherical TiO₂ (Degauusa P25) electrodes. The electrodes with nanospheroidal morphology showed better device performance than the P25 nanoparticle electrodes primarily due to both better connectivity among nanospheroidal TiO₂ particles and larger mesopores, resulting in deeper penetration of the electrolyte in QD-sensitized solar cells.     

Cadmium and copper absorption mediated by a poly(vinyl alcohol)‐b‐polyacrylonitrile based micelle/Trichosporon cutaneum cell system

The micelles of a recently synthesized copolymer of poly(vinyl alcohol)‐b‐polyacrylonitrile added to the growth solution of the filamentous yeast Trichosporon cutaneum strain R57 led to the formation of a binary system consisting of micelles and cells. The resulting micelle/cell system was studied as a model for the removal of toxic concentrations of heavy‐metal ions (cadmium and copper) from aqueous solutions. The ion‐removal efficiency mediated by this system was higher than for free‐floating cells. The copper‐removal efficiency from the solution reached a level of 65% after 24 h of cultivation, whereas the cadmium‐removal efficiency reached 62% after 6 h of growth. For comparison, the free‐floating cells removed 42% of copper and only 38% of cadmium from the solutions. The effects of surface interactions between the cells and polymer micelles on the biosorption capacity of the cells are discussed in the article. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Direct Generation of Mn‐Doped ZnS Quantum Dots/Alginate Nanocomposite Beads Based on Gelation and In Situ Synthesis of Quantum Dots

Herein, a concise and novel method is developed to directly generate Mn‐doped ZnS QDs/alginate nanocomposite beads. In this method, the ionic gelation of alginate is employed to produce alginate gel beads in a solution of Zn²⁺ and Mn²⁺ ions. Subsequently, the gel beads serve as the reaction support for in situ synthesis of Mn‐doped ZnS QDs in the beads through the reaction of sodium sulfide with Zn²⁺ and Mn²⁺ ions. The method has many benefits such as the simple preparation, the environmentally friendly process, the mild conditions, and the easy post‐treatment for the beads. The resulting QDs/alginate beads are homogeneous and stable gel spheres which show clear fluorescence. TEM images demonstrate that Mn‐doped ZnS QDs are homogeneously distributed within the QDs/alginate nanocomposite, and their average size is 2.4 ± 0.3 nm. Potentially, the QDs/alginate beads can be utilized for fluorescence bioimaging, as well as fluorescence detection toward metal ions.     

Cadmium sulfide activated zinc oxide coatings deposited by liquid plasma spray for room temperature nitrogen dioxide detection under visible light illumination

Zinc oxide (ZnO) is well-known to be used as a gas sensing material. However, due to its high operation temperature, the chemical and thermal stability of ZnO based gas sensors are relatively low. In recent years, some researchers adopt light illumination as activated source to replace heating and obtain high gas sensing performance at low temperature. The study that follows is an attempt to use cadmium sulfide (CdS) as sensitizer to activate ZnO at room temperature with assistance of visible-light illumination. CdS–ZnO coatings were deposited by liquid plasma spray with aqueous solution containing zinc acetate and cadmium sulfide as precursors. The crystal structure of as-sprayed CdS–ZnO coatings was characterized by X-ray diffractometer (XRD) and field-emission scanning electron microscopy (FE-SEM). The sensing performance of sensors based on CdS–ZnO coatings were tested with 1 ppm nitrogen dioxide (NO₂) at room temperature illuminated under various visible lights. The results demonstrated that the LPS process was a straightforward method for deposition of high performance CdS–ZnO sensitive layers and the obtained sensors showed high responses to NO₂ at room temperature.     

Activity of horseradish peroxidase in aqueous and reverse micelles and back‐extraction from reverse‐micellar phases

Studies on the activity of the enzyme horseradish peroxidase (HRP) have been carried out in micellar as well as reverse‐micellar media. The activity of the enzyme was studied in the presence of different classes of surfactants – ionic as well as non‐ionic. In aqueous media, the activity of the enzyme varied depending on whether the concentration of the surfactant used was above or below the critical micellar concentration (CMC). The enzyme was also studied in reverse‐micellar systems. HRP was introduced into the reverse micellar phase by the injection method and its activity within the reverse micelles was determined. The effect of water to surfactant ratio (W_o) on activity within reverse micelles was studied, and an almost two‐fold increase in activity was seen when the enzyme was encapsulated within reverse micelles of aqueous phase fractional hold‐up (?) of 0.0072 (v/v) consisting of sodium bis‐(2‐ethylhexyl) sulfosuccinate (AOT) in isooctane at a W_o of 20. The activity of HRP was measured over a wide range of AOT concentrations having different W_o values. Back‐extraction of HRP from these reverse micelles was carried out at varying ionic strengths of phosphate buffer. Back extraction was found to be highest at pH 7.0 in 40 mol m^?3 phosphate buffer and 100 mol m^?3 sodium chloride. © 2001 Society of Chemical Industry     

Preparation and Characterization of Highly Fluorescent, Glutathione-coated Near Infrared Quantum Dots for in Vivo Fluorescence Imaging

Fluorescent probes that emit in the near-infrared (NIR, 700–1,300 nm) region are suitable as optical contrast agents for in vivo fluorescence imaging because of low scattering and absorption of the NIR light in tissues. Recently, NIR quantum dots (QDs) have become a new class of fluorescent materials that can be used for in vivo imaging. Compared with traditional organic fluorescent dyes, QDs have several unique advantages such as size- and composition-tunable emission, high brightness, narrow emission bands, large Stokes shifts, and high resistance to photobleaching. In this paper, we report a facile method for the preparation of highly fluorescent, water-soluble glutathione (GSH)-coated NIR QDs for in vivo imaging. GSH-coated NIR QDs (GSH-QDs) were prepared by surface modification of hydrophobic CdSeTe/CdS (core/shell) QDs. The hydrophobic surface of the CdSeTe/CdS QDs was exchanged with GSH in tetrahydrofuran-water. The resulting GSH-QDs were monodisperse particles and stable in PBS (phosphate buffered saline, pH = 7.4). The GSH-QDs (800 nm emission) were highly fluorescent in aqueous solutions (quantum yield = 22% in PBS buffer), and their hydrodynamic diameter was less than 10 nm, which is comparable to the size of proteins. The cellular uptake and viability for the GSH-QDs were examined using HeLa and HEK 293 cells. When the cells were incubated with aqueous solutions of the GSH-QDs (10 nM), the QDs were taken into the cells and distributed in the perinuclear region of both cells. After 12 hrs incubation of 4 nM of GSH-QDs, the viabilities of HeLa and HEK 293 cells were ca. 80 and 50%, respectively. As a biomedical utility of the GSH-QDs, in vivo NIR-fluorescence imaging of a lymph node in a mouse is presented.     

In situ preparation of CdS/PVA nanocomposites using gamma radiation

Films of poly(vinyl alcohol)/cadmium sulphide (PVA/CdS) nanocomposite containing various concentrations of Cd²⁺ ions were prepared using gamma radiation at different doses from 50 up to 200 kGy. The UV/VIS spectra revealed that the CdS/PVA nanocomposites showed blue shift for the absorption peak as compared with bulk CdS. As the irradiation dose increased, a gradual red shift in the wavelength accompanying with broadening of the absorption peak was observed. The estimated optical band gap energies and the calculated CdS particle sizes of (PVA/CdS) showed correlation between their values and the variable parameters (irradiation dose and Cd⁺²:S^?2 molar ratio). Transmission electron microscopy images showed that the CdS/PVA nanocomposites were dispersed as spherical CdS nanoparticles with homogeneity at either lower concentration of CdCl₂ or irradiation dose. The nano‐rod structures of CdS was accompanied with small agglomeration at either higher CdCl₂ concentration or irradiation dose. A cubic phase and mixture of cubic and hexagonal phases of the prepared CdS nanoparticles were formed at lower and higher CdCl₂ concentrations, respectively. Fourier Transform Infrared spectra confirmed the coordination of CdS nanoparticles with the hydroxyl groups of PVA matrix. POLYM. ENG. SCI., 55:2583–2590, 2015. © 2015 Society of Plastics Engineers