Photoassisted synthesis of CdSe and core-shell CdSe/CdS quantum dots

This paper describes the synthesis of core-shell CdSe/CdS quantum dots (QDs) in aqueous solution by a simple photoassisted method. CdSe was prepared from cadmium nitrate and 1,1-dimethylselenourea precursors under illumination for up to 3 h using a pulsed Nd:YAG laser at 532 nm. The effects that the temperature and the laser irradiation process have on the synthesis of CdSe were monitored by a series of experiments using the precursors at a Cd:Se concentration ratio of 4. Upon increasing the temperature (80-140 degrees C), the size of the CdSe QDs increases and the time required for reaching a maximum photoluminescence (PL) is shortened. Although the as-prepared CdSe QDs possess greater quantum yields (up to 0.072%) compared to those obtained by microwave heating (0.016%), they still fluoresce only weakly. After passivation of CdSe (prepared at 80 degrees C) by CdS using thioacetamide as the S source (Se:S concentration ratio of 1) at 80 degrees C for 24 h, the quantum yield of the core-shell CdSe/CdS QDs at 603 nm is 2.4%. Under UV irradiation of CdSe/CdS for 24 h using a 100-W Hg-Xe lamp, the maximum quantum yield of the stable QDs is 60% at 589 nm. A small bandwidth (W1/2 < 35 nm) indicates the narrow size distribution of the as-prepared core-shell CdSe/CdS QDs. This simple photoassisted method also allows the preparation of differently sized (3.7-6.3-nm diameters) core-shell CdSe/CdS QDs that emit in a wide range (from green to red) when excited at 480 nm.     

One‐Pot Synthesis of CdSe Quantum Dots in Aqueous Solution for Biological Labeling

The one‐pot synthesis of water‐soluble and biologically compatible yellow CdSe quantum dots (QDs) featuring the use of glutathione (GSH) as the capping and reducing agent was achieved under aqueous conditions at 150 °C. The synthesized yellow CdSe QDs with quantum yield (QY) up to 20% exhibit zinc blende cubic structure particles with an average diameter of 4‐5 nm. It was found that both molar ratio of Se/Cd and reaction time had a significant effect on size distribution of GSH‐CdSe QDs. Meanwhile, the interaction of QDs bioconjugated to bovine hemoglobin (BHb) was studied by absorption and fluorescence(FL) spectra. With addition of BHb, the FL intensity of CdSe QDs largely quenched due to the static mechanism. The linear range is 5.0 × 10^?8 mol/L to 3.0 × 10^?6 mol/L, and the correlation coefficient is 0.9991, suggesting that could be used as a probe to label biological molecules and bacterial cells.     

Forming water-soluble CdSe/ZnS QDs using amphiphilic polymers, stearyl methacrylate/methylacrylate copolymers with different hydrophobic moiety ratios and their optical properties and stability

The amphiphilic stearyl methacrylate/methylacrylic acid copolymers (PSMs) were used as phase transfer reagents to convert CdSe/ZnS core-shell quantum dots (QDs) in chloroform to water-soluble PSMs-coated quantum dots (PSM-QDs). The optical properties and stability of PSM-QDs were influenced by the hydrophobic moiety ratios of PSMs, the PSM/QDs mass/volume ratio and the reaction time. The resulting PSM-QDs on optimum reaction conditions retained 60% of the photoluminescence value of the original CdSe/ZnS QDs in chloroform. The carboxylate-based PSM-QDs survived UV irradiation in air for at least 15 days. Upon UV irradiation, the PSM-QDs became about 2 times brighter than the original CdSe/ZnS QDs in chloroform, and the UV-brightened PL can retain the brightness for at least several months. Experimental results further confirmed the stability of PSM-QDs against strong acid, photochemical and thermal treatments. In addition to good performance of PSM-QDs, the synthesis of PSM and the corresponding water-soluble QDs is relatively simple.     

Effects of nanoscale quantum dots in male Chinese loaches (<Emphasis Type="Italic">Misgurnus anguillicaudatus</Emphasis>): Estrogenic interference action,toxicokinetics and oxidative stress

Quantum dots (QDs) have more and more attention as a novel example of nanocrystals due to their unique fluorescent characteristics. Recently, the toxicity and the potential environmental effects of QDs have become a research hotspot. In this work, in vivo endocrine disrupting effect, toxicokinetics and oxidative stress of QDs were characterized following the intraperitoneal dosing in Chinese loaches. Vitellogenin (Vtg) levels induced by E2 decreased significantly when administrated with the mixture of QDs and E2, which was consistent with the observations of histopathology in testes. The release of free Cd²⁺ from QDs and the non-specific adsorption of E2 by QDs might be the joint factors contributing to the inhibition of Vtg expression induced by E2 in the male Chinese loaches. In the muscle, bone, intestines, blood and testis, CdSe QDs reached the maximal concentration (C _max) in approximately 1-h postinjection and subsequently presented downtrend with the prolonged time. Whereas, there were even increasing tendencies of CdSe QDs’ concentrations in the liver and kidney. It is educible that CdSe QDs can be persistent at least for 7 days, indicating the overall half-life of CdSe QDs in the fish body is very long. The measurement of hepatic superoxide dismutase (SOD) activity and reduced glutathione (GSH) content indicate that QDs have smaller effects on the antioxidative system of the organisms compared with free Cd²⁺ due to the effective prevention of the release of Cd by PEG coating of QDs. The comprehensive evaluation of QDs’ toxicity in the present study provides an essential and general framework towards more focused research on the elucidation of the biological effects of QDs in vivo.     

Electrochemical biosensing for dsDNA damage induced by PbSe quantum dots under UV irradiation

<正>An electrochemical sensor for the detection of the natural double-stranded DNA(dsDNA) damage induced by PbSe quantum dots(QDs) under UV irradiation was developed.The biosensing membranes were prepared by successively assembling 3- mercaptopropionic acid,polycationic poly(diallyldimethyl ammonium) and dsDNA on the surface of the gold electrode.Damage of dsDNA was fulfilled by immersing the sensing membrane electrode in PbSe QDs suspension and illuminating it with an UV lamp. Cyclic voltammetry was utilized to detect dsDNA damage with Co(phen)_3~(3+) as the electroactive probe.The UV irradiation,Pb~(2+) ions liberated from the PbSe QDs under the UV irradiation and the reactive oxygen species(ROS) generated in the presence of the PbSe QDs also under the UV irradiation were the three factors of inducing the dsDNA damage.The synergistic effect of the three factors might dramatically enhance the damage of dsDNA.This electrochemical sensor provided a simple method for detecting DNA damage,and may be used for investigating the DNA damage induced by other QDs.     

Synthesis of Mn-doped zinc blende CdSe nanocrystals for quantum dot-sensitized solar cells

Mn-doped CdSe quantum dots (QDs) with a zinc blende structure were synthesized via a phosphine-free method in octadecene (ODE) and oleic acid. The structure, size, morphology, and optical property of the QDs were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV–visible absorption spectra (UV–Vis), respectively. The QDs were assembled onto a microporous TiO₂ photoanode by an ex situ ligand exchange route. Quantum dot-sensitized solar cells (QDSCs) based on the above-synthesized QDs and polysulfide electrolytes were fabricated. The photovoltaic performance and impedance of the CdSe and Mn-doped CdSe QDSCs were further investigated. An improvement in efficiency to 1.84 % was achieved as compared with 0.94 % for the QDSCs based on the pure CdSe QDs. The improvement was ascribed to the existence of long-lived high-energy doping levels on the large-sized Mn-doped CdSe QDs, which provides a significant driving force for faster charge separation and electron transfer.     

The Application of CdSe Quantum Dots with Multicolor Emission as Fluorescent Probes for Cell Labeling

Herein, highly luminescent CdSe quantum dots (QDs) with emissions from the blue to the red region of visible light were synthesized by using a simple method. The emission range of the CdSe QDs could be tuned from λ=503 to 606 nm by controlling the size of the CdSe QDs. Two amino acids, L ‐tryptophan (L ‐Trp) and L ‐arginine (L ‐Arg), were used as coating agents. The quantum yield (QY) of CdSe QDs (green color) with an optimized thickness could reach up to 52 %. The structures and compositions of QDs were examined by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Optical properties were studied by using UV/Vis and photoluminescence (PL) spectroscopy and a comparison was made between uncoated and coated CdSe QDs. The amino acid‐modified β‐cyclodextrin (CD)‐coated CdSe QDs presented lower cytotoxicity to cells for 48 h. Furthermore, amino acid‐modified β‐CD‐coated green CdSe QDs in HepG2 cells were assessed by using confocal laser scanning fluorescence microscopy. The results showed that amino acid‐modified β‐CD‐coated green CdSe QDs could enter tumor cells efficiently and indicated that biomolecule‐coated QDs could be used as a potential fluorescent probe.     

Optimized Synthesis and Fluorescence Spectrum Analysis of CdSe Quantum Dots

An optimized synthesis route was applied for controlling the preparation of CdSe quantum dots (QDs) in an aqueous solution. Some key factors which influencing the properties of CdSe QDs, such as initial pH, stabilizers, ratio of precursor, etc. were investigated. The size, shape, crystal structure, and optical property of CdSe QDs were also characterized by TEM, XRD, UV-Vis, and fluorescence (FL) spectra. The result showed that high-quality cubic CdSe QDs with 3 nm were obtained. The experiments also confirmed that thioglycolic acid (TGA), under the conditions of weak acid, is a better stabilizer than others. The ratio of [Cd²⁺] to [SeSO₃ ^2?] played an important role in the formation of CdSe QDs. The mechanisms about the influence factors were also presented.     

Electrochemiluminescence Sensor for Phosphate Ions Based on Europium(III)‐Modulated CdSe Quantum Dots

Phosphate anions are determined based on the electrochemiluminescence (ECL) of CdSe quantum dots (CdSe QDs) capped with 3‐mercaptopropionic acid. The ECL gets quenched with the introduction of Eu³⁺ ions, but it is restored on the further addition of phosphate anions. The sensing mechanism might be due to the strong and specific interaction between phosphate anions and the Eu³⁺ ions, leading to the releasing of CdSe QDs from aggregates. On the basis of the quenching/recovery ECL behaviors, the ECL sensor offer acceptable sensitivity, high selectivity, and a linear response from 0.1 to 120 µM with a detection limit of 0.03 µM (3δ) for phosphate anions.     

Surface‐State‐Mediated Charge‐Transfer Dynamics in CdTe/CdSe Core–Shell Quantum Dots

Herein, we report the synthesis of aqueous CdTe/CdSe type‐II core–shell quantum dots (QDs) in which 3‐mercaptopropionic acid is used as the capping agent. The CdTe QDs and CdTe/CdSe core–shell QDs are characterized by X‐ray diffraction (XRD), high‐resolution transmission electron microscopy (HR‐TEM), steady‐state absorption, and emission spectroscopy. A red shift in the steady‐state absorption and emission bands is observed with increasing CdSe shell thickness over CdTe QDs. The XRD pattern indicates that the peaks are shifted to higher angles after growth of the CdSe shell on the CdTe QDs. HR‐TEM images of both CdTe and CdTe/CdSe QDs indicate that the particles are spherical, with a good shape homogeneity, and that the particle size increases by about 2 nm after shell formation. In the time‐resolved emission studies, we observe that the average emission lifetime (τ_av) increases to 23.5 ns for CdTe/CdSe (for the thickest shell) as compared to CdTe QDs (τ_av=12 ns). The twofold increment in the average emission lifetime indicates an efficient charge separation in type‐II CdTe/CdSe core–shell QDs. Transient absorption studies suggest that both the carrier cooling and the charge‐transfer dynamics are affected by the presence of traps in the CdTe QDs and CdTe/CdSe core–shell QDs. Carrier quenching experiments indicate that hole traps strongly affect the carrier cooling dynamics in CdTe/CdSe core–shell QDs.     

Recognition of DNA based on changes in the fluorescence intensity of CdSe/CD QDs–phenanthroline systems

The CdSe quantum dots (QDs) modified by mercapto-β-cyclodextrin (CD) were synthesized and characterized by transmission electron microscopy, powder X-ray diffraction, excitation and emission spectra, and fluorescence lifetime. When λ_ex = 370 nm, the fluorescence peak of CdSe/CD QDs is at 525 nm. Phenanthroline (Phen) is able to quench their fluorescence, which can be recovered by the addition of DNA. The quenching and restoration of fluorescence intensity were found to be linearly proportional to the amount of Phen and DNA, respectively. The variation of the fluorescence intensity of the CdSe/CD QDs–Phen system was studied, and it was demonstrated to result from a static mechanism due to the formation of a Phen inclusion complex with the CdSe QDs modified by mercapto-β-cyclodextrin. The fluorescence recovery was due to the binding of DNA with Phen in the inclusion complex, leading to the freeing of the CdSe/CD QDs. The binding constants and sizes of the binding sites of the Phen–DNA interaction were calculated to be 1.33 × 10⁷ mol^?1 L and 10.79 bp.     

Continuous‐Flow Synthesis of CdSe Quantum Dots: A Size‐Tunable and Scalable Approach

In recent years, continuous‐flow/microreactor processing for the preparation of colloidal nanocrystals has received considerable attention. The intrinsic advantages of microfluidic reactors have opened new opportunities for the size‐controlled synthesis of nanocrystals either in the laboratory or on a large scale. Herein, an experimentally simple protocol for the size‐tunable continuous‐flow synthesis of rather monodisperse CdSe quantum dots (QDs) is presented. CdSe QDs are manufactured by using cadmium oleate as cadmium source, selenium dioxide as selenium precursor, and 1‐octadecene as solvent. Exploiting selenium dioxide as selenium source and 1‐octadecene as solvent allows execution of the complete process in open air without any requirement for air‐free manipulations using a glove box or Schlenk line. Continuous‐flow processing is performed with a stainless steel coil of 1.0 mm inner diameter pumping the combined precursor solution through the reactor by applying a standard HPLC pump. The effect of different reaction parameters, such as temperature, residence time, and flow rate, on the properties of the resulting CdSe QDs was investigated. A temperature increase from 240 to 260 °C or an extension of the residence time from 2 to 20 min affords larger nanocrystals (range 3–6 nm) whereas the size distribution does not change significantly. Longer reaction times and higher temperatures result in QDs with lower quantum yields (range 11–28 %). The quality of the synthesized CdSe QDs was confirmed by UV/Vis and photoluminescence spectroscopy, small‐angle X‐ray scattering, and high‐resolution transmission electron microscopy. Finally, the potential of this protocol for large‐scale manufacturing was evaluated and by operating the continuous‐flow process for 87 min it was possible to produce 167 mg of CdSe QDs (with a mean diameter of 4 nm) with a quantum yield of 28 %.     

Study the damage of DNA molecules induced by three kinds of aqueous nanoparticles

In this paper, the interaction of DNA molecules with aqueous CdTe quantum dots (CdTe QDs), CdTe/SiO₂ composite nanoparticles (CdTe/SiO₂ NPs), and Mn-doped ZnSe quantum dots (Mn:ZnSe d-dots) was studied with ethidium bromide as a probe. The purpose of this work was to study the damage of DNA molecules induced by these three kinds of water-soluble nanoparticles. It was found that ionic strength, pH value and UV irradiation influenced the PL emission properties of CdTe QDs, CdTe/SiO₂ NPs and Mn:ZnSe d-dots, and also influenced the interaction of DNA molecules with them. Among the three kinds of nanoparticles, DNA molecules were most easily damaged by CdTe QDs whether in the dark or under UV irradiation. The CdTe/SiO₂ NPs led to much less DNA damage when compared with CdTe QDs, as a silica overcoating layer could isolate the QDs from the external environment. Mn:ZnSe d-dots as a new class of non-cadmium doped QDs demonstrated almost no damage for DNA molecules, which have great potentials as fluorescent labels in the applications of biomedical assays, imaging of cells and tissues, even in vivo investigations.     

Enhancing the device performance of a blue light‐emitting copolymer using CdSe/ZnS quantum dots

An alternating triarylamine‐functionalized fluorene‐based copolymer synthesized using a Suzuki–Miyaura cross‐coupling procedure is used as blue emitting layer in polymer light‐emitting diodes (PLEDs). Subsequently, the effects of CdSe/ZnS quantum dots (QDs) on the optoelectronic properties of the copolymer are investigated. Therefore, CdSe/ZnS QDs are embedded into the copolymer matrix and hybrid PLEDs are fabricated. The devices comprised of CdSe/ZnS QDs reveal enhanced performances, yielding about 3.4 times more luminous efficiency than that of the device without QDs. Further enhancement is achieved by using electron transport layer; the luminous efficiency rose from 0.065 to 1.740 cd A^?1 for the hybrid PLEDs, corresponding to a superb 27‐fold intensification of the efficiency. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 147–156     

Optical properties of CdSe and CdSe/ZnS quantum dots dispersed in solvents of different polarity

Original organic capping TOPO/TOP groups of CdSe and CdSe/ZnS quantum dots (QDs), from mother solution were replaced with 2_mercaptoethanol, which was chosen as model compound, in order to achieve water solubility. Obtained water dispersions of CdSe and CdSe/ZnS QDs were characterized by UV/VIS absorption and luminescence techniques. Luminescence measurements revealed that bare cores are very sensitive to surface capping, transfer into water diminished emission intensity. Core/shell, CdSe/ZnS, QDs are much more resistant to changes of the capping and solvent, and significant part of emission intensity was preserved in water. The article is published in the original.     

Controlled synthesis of CdSe quantum dots by a microwave-enhanced process: a green approach for mass production

A method that does not employ hot-injection techniques has been developed for the size-tunable synthesis of high-quality CdSe quantum dots (QDs) with zinc blende structure. In this environmentally benign synthetic route, which uses less toxic precursors, solvents, and capping ligands, CdSe QDs that absorb visible light are obtained. The size of the as-prepared CdSe QDs and thus their optical properties can be manipulated by changing the microwave reaction conditions. The QDs were characterized by XRD, TEM, UV/Vis, FTIR, time-resolved fluorescence spectroscopy, and fluorescence spectrophotometry. In this approach, the reaction is conducted in open air and at a much lower temperature than in hot-injection techniques. The use of microwaves in this process allows for a highly reproducible and effective synthesis protocol that is fully adaptable for mass production and can be easily employed to synthesize a variety of semiconductor QDs with the desired properties. Possible applications of the CdSe QDs were assessed by deposition on TiO(2) films.     

CdSe Quantum Dots and N719‐Dye Decorated Hierarchical TiO2 Nanorods for the Construction of Efficient Co‐Sensitized Solar Cells

Three‐dimensional hierarchical TiO₂ nanorods (HTNs) decorated with the N719 dye and 3‐mercaptopropionic or oleic acid capped CdSe quantum dots (QDs) in photoanodes for the construction of TiO₂ nanorod‐based efficient co‐sensitized solar cells are reported. These HTN co‐sensitized solar cells showed a maximum power‐conversion efficiency of 3.93 %, and a higher open‐circuit voltage and fill factor for the photoanode with 3‐mercaptopropionic acid capped CdSe QDs due to the strong electronic interactions between CdSe QDs, N719 dye and HTNs, and the superior light‐harvesting features of the HTNs. An electrochemical impedance analysis indicated that the superior charge‐collection efficiency and electron diffusion length of the CdSe QD‐coated HTNs improved the photovoltaic performance of these HTN co‐sensitized solar cells.     

Study on the interaction between CdSe quantum dots and chitosan by scattering spectra

Two different stabilizing agents thioglycolic acid (TGA) and l-cysteine (l-Cys) capped CdSe QDs with the diameter of 2 nm were synthesized, large amounts of stabilizing agents connected to CdSe QDs surface through Cd–S bond. The interaction between chitosan and QDs had been investigated, respectively. The interaction lead to the remarkable enhancement of RRS, RNLS and the enchantments were in proportional to the concentration of chitosan in a certain range. Under the optimal conditions, compared with TGA–CdSe QDs, the interaction between l-Cys–CdSe QDs with chitosan owned more broad linear range 0.042–3.0 μg mL⁻¹ and lower detect limits 1.2 ng mL⁻¹. The influences of factors on the interaction between chitosan with QDs and some foreign substances were all examined, which showed that the methods had a good sensitivity and selectivity. Based on this, it is hoped to build a method for the determination of chitosan using CdSe QDs as probes. Through Fourier transform infrared spectroscopy (FTIR) transmission electron microscopy (TEM), it was speculated that CdSe QDs interacted with chitosan to form a network structure aggregates through electrostatic attraction and hydrophobic forces. The reasons for the enhancement of RRS intensity were assumed as follows: resonance enhanced Rayleigh scattering effect, increase of the molecular volume, and hydrophobic effect.     

Study on the interaction between CdSe quantum dots and hemoglobin

The interaction between CdSe quantum dots (QDs) and hemoglobin (Hb) was investigated by ultraviolet and visible (UV-vis) absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and fluorescence (FL) spectroscopy. The intensity of UV-vis absorption spectrum of a mixture of CdSe QDs and Hb was obviously changed at the wavelength of 406nm at pH 7.0, indicating that CdSe QDs could bind with Hb. The influences of some factors on the interactions between CdSe QDs and Hb were studied in detail. The binding molar ratio of CdSe QDs and Hb was 12:1 by a mole-ratio method. The mechanism of the interaction between CdSe QDs and Hb was also discussed.     

Mechanistic Insights into the Interface‐Directed Transformation of Thiols into Disulfides and Molecular Hydrogen by Visible‐Light Irradiation of Quantum Dots

Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible‐light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H₂ without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground‐state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants.