Luminescent CdS quantum dots as selective ion probes

Water-soluble luminescent CdS quantum dots (QDs) capped by polyphosphate, L-cysteine, and thioglycerol were synthesized in aqueous solution. The ligands were found to have a profound effect on the luminesence response of CdS QDs to physiologically important metal cations. Polyphosphate-capped CdS QDs were sensitive to nearly all mono- and divalent cations, showing no ion selectivity. Conversely, thioglycerol-capped CdS QDs were sensitive to only copper and iron ions. Similar concentrations of physiologically relevant cations, such as zinc, sodium, potassium, calcium, and magnesium ions did not affect the luminescence of thioglycerol-capped CdS QDs. On the other hand, L-cysteine-capped CdS QDs were sensitive to zinc ions and insensitive to other physiologically important cations, such as copper, calcium, and magnium ions. To demonstrate the detection capability of these new ion probes, L-cysteine and thioglycerol-capped CdS QDs were used to detect zinc and copper ions in physiological buffer samples. The detection limits were 0.8 microM for zinc (II) and 0.1 microM for copper (II) ions. The emission enhancement of the QDs by zinc (II) is attributed to activation of surface states, whereas the effective reduction of copper (II) to copper (I) may explain the emission decrease of the thioglycerol-capped CdS QDs when charged with copper ions. Unlike organic fluorescent dyes, the thioglycerol-capped luminescent CdS QDs discriminate between copper and zinc ions and are therefore suitable for the analysis of copper ions in biological samples in the presence of physiological concentrations of zinc ions. The interference of iron ions with zinc and copper ion detection is attributed to an inner filter effect, which is eliminated by adding fluoride ions to form the colorless complex FeF6(3-). To the best of our knowledge, this is first use of luminescent semiconductor quantum dots as selective ion probes in aqueous samples.     

Versatile immunosensor using CdTe quantum dots as electrochemical and fluorescent labels

A versatile immunosensor using CdTe quantum dots as electrochemical and fluorescent labels has been developed for sensitive protein detection. This sandwich-type sensor is fabricated on an indium tin oxide chip covered with a well-ordered gold nanoparticle monolayer. Gel imaging systems were successfully introduced to develop a novel high-efficient optical immunoassay, which could perform simultaneous detection for the samples with a series of different concentrations of a target analyte. The linear range of this assay was between 0.1 and 500 ng/mL, and the assay sensitivity could be further increased to 0.005 ng/mL with the linear range from 0.005 to 100 ng/mL by stripping voltammetric analysis. The immunosensor showed good precision, high sensitivity, acceptable stability, and reproducibility and could be used for the detection of real sample with consistent results in comparison with those obtained by the ELISA method.     

Semiconductor quantum rods as single molecule fluorescent biological labels

In this paper, we report the development of rod-shaped semiconductor nanocrystals (quantum rods) as fluorescent biological labels. Water-soluble biocompatible quantum rods have been prepared by surface silanization and applied for nonspecific cell tracking as well as specific cellular targeting. Quantum rods are brighter single molecule probes as compared to quantum dots. They have many potential applications as biological labels in situations where their properties offer advantages over quantum dots.     

A new class of far-red and near-infrared biological labels based on alloyed semiconductor quantum dots

Ternary cadmium selenium telluride quantum dots (CdSe(1-x)Tex, x = mole fraction of tellurium) have been prepared for potential use as constant-size biolabels with tunable fluorescence emission in the far-red and near-infrared (650-850 nm) spectral range. In contrast to particle size tuning reported for binary dots, we show that molar composition can be used to tune the optical and electronic properties of alloyed semiconductor nanocrystals without changing the particle size. A surprising finding is a nonlinear relationship between the composition and the absorption/emission energies, leading to new properties not obtainable from the parent CdSe and CdTe binary systems. Coating the alloy cores with a higher band-gap material such as CdS improves the fluorescence efficiencies to about 40-60% at room temperature and allows the preparation of water-soluble and biocompatible alloyed dots at similar quantum yields. A cadmium-rich surface is found to improve mercapto ligand binding and the long-term stability of water-soluble dots.     

Photophysics of dopamine-modified quantum dots and effects on biological systems

Semiconductor quantum dots (QDs) have been widely used for fluorescent labelling. However, their ability to transfer electrons and holes to biomolecules leads to spectral changes and effects on living systems that have yet to be exploited. Here we report the first cell-based biosensor based on electron transfer between a small molecule (the neurotransmitter dopamine) and CdSe/ZnS QDs. QD-dopamine conjugates label living cells in a redox-sensitive pattern: under reducing conditions, fluorescence is only seen in the cell periphery and lysosomes. As the cell becomes more oxidizing, QD labelling appears in the perinuclear region, including in or on mitochondria. With the most-oxidizing cellular conditions, QD labelling throughout the cell is seen. Phototoxicity results from the creation of singlet oxygen, and can be reduced with antioxidants. This work suggests methods for the creation of phototoxic drugs and for redox-specific fluorescent labelling that are generalizable to any QD conjugated to an electron donor.     

Fabrication and characterization of silicon quantum dots in Si-rich silicon carbide films

Amorphous Si-rich silicon carbide films were prepared by magnetron co-sputtering and subsequently annealed at 900-1100 degrees C. After annealing at 1100 degrees C, this configuration of silicon quantum dots embedded in amorphous silicon carbide formed. X-ray photoelectron spectroscopy was used to study the chemical modulation of the films. The formation and orientation of silicon quantum dots were characterized by glancing angle X-ray diffraction, which shows that the ratio of silicon and carbon significantly influences the species of quantum dots. High-resolution transmission electron microscopy investigations directly demonstrated that the formation of silicon quantum dots is heavily dependent on the annealing temperatures and the ratio of silicon and carbide. Only the temperature of about 1100 degrees C is enough for the formation of high-density and small-size silicon quantum dots due to phase separation and thermal crystallization. Deconvolution of the first order Raman spectra shows the existence of a lower frequency peak in the range 500-505 cm(-1) corresponding to silicon quantum dots with different atom ratio of silicon and carbon.     

Confinement effects and tunnelling through quantum dots

Several recent theoretical advances concerning semiconductor quantum dots are reviewed. First of all, the effect of the quantum confinement on the energy gap is revisited on the basis of GW and Bethe-Salpeter calculations, showing that the excitonic gap is practically equal to the ordinary eigenvalue gap of single-particle approximations. The second part demonstrates that it is now possible to calculate the conductance peaks for the tunnelling current through a nanostructure. Finally, we discuss in some detail the concept of a macroscopic dielectric constant for nanostructures, showing that, except for a thin surface layer, the local dielectric constant still keeps its bulk value down to pretty small nanostructures.     

Luminescent properties and excitation mechanism of ZnSe quantum dots embedded in ZnS Matrix

In this paper, we report alternative-current thin film electroluminescence structure with ZnSe quantum dots embedded in ZnS matrix as light-emitting center, i.e., ITO/SiO_x (100 nm)/[ZnS (10 nm)/ZnSe (1 nm)]₃₀/SiO_x (100 nm)/Al. Blue emissions at 390 and 477 nm are obtained in its alternative-current electroluminescent spectra. By studying its luminescent spectroscopy and brightness oscillogram of the device, we found that blue emission came from defect states at ZnSe/ZnS interface and the excitation mechanism was hot-electron impact.     

Freestanding silicon quantum dots: origin of red and blue luminescence

In this paper, we studied the behavior of silicon quantum dots (Si-QDs) after etching and surface oxidation by means of photoluminescence (PL) measurements, Fourier transform infrared spectroscopy (FTIR) and electron paramagnetic resonance spectroscopy (EPR). We observed that etching of red luminescing Si-QDs with HF acid drastically reduces the concentration of defects and significantly enhances their PL intensity together with a small shift in the emission spectrum. Additionally, we observed the emergence of blue luminescence from Si-QDs during the re-oxidation of freshly etched particles. Our results indicate that the red emission is related to the quantum confinement effect, while the blue emission from Si-QDs is related to defect states at the newly formed silicon oxide surface.     

Luminescent quantum dots fluorescence resonance energy transfer-based probes for enzymatic activity and enzyme inhibitors

The paper describes the development and characterization of analytical properties of quantum dot-based probes for enzymatic activity and for screening enzyme inhibitors. The luminescent probes are based on fluorescence resonance energy transfer (FRET) between luminescent quantum dots that serve as donors and rhodamine acceptors that are immobilized to the surface of the quantum dots through peptide linkers. Peptide-coated CdSe/ZnS quantum dots were prepared using a one-step ligand exchange process in which RGDC peptide molecules replace trioctylphosphine oxide (TOPO) molecules as the capping ligands of the quantum dots. The peptide molecules were bound to the surface of the CdSe/ZnS quantum dots through the thiol group of the peptide cysteine residue. The peptide-coated quantum dots were labeled with rhodamine to form the FRET probes. The emission quantum yield of the quantum dot FRET probes was 4-fold lower than the emission quantum yield of TOPO-capped quantum dots. However, the quantum dot FRET probes were sufficiently bright to enable quantitative enzyme and enzyme inhibition assays. The probes were used first to test the enzymatic activity of trypsin in solution based on FRET signal changes of the quantum dot-based enzymatic probes in the presence of proteolytic enzymes. For example, exposure of the quantum dot FRET probes to 500 microg/mL trypsin for 15 min resulted in 60% increase in the photoluminescence of the quantum dots and a corresponding decrease in the emission of the rhodamine molecules. These changes resulted from the release of rhodamine molecules from the surface of the quantum dots due to enzymatic cleavage of the peptide molecules. The quantum dot FRET-based probes were used to monitor the enzymatic activity of trypsin and to screen trypsin inhibitors for their inhibition efficiency.     

Free standing luminescent silicon quantum dots: evidence of quantum confinement and defect related transitions

We report the synthesis of luminescent, free standing silicon quantum dots by dry and wet etching of silicon and silicon oxide core/shell nanostructures, which are synthesized by controlled oxidation of mechanically milled silicon. Dry and wet etching performed with CF(4) plasma and aqueous HF, respectively, result in the removal of the thick oxide shell of the core/shell nanostructures and affect an additional step of size reduction. HF etch is capable of producing isolated, spherical quantum dots of silicon with dimensions ～ 2 nm. However, the etching processes introduce unsaturated bonds at the surface of the nanocrystals which are subsequently passivated by oxygen on exposure to ambient atmosphere. The photoluminescence spectra of the colloidal suspensions of these nanocrystals are characterized by double peaks and excitation dependent shift of emission energy. Comparison of the structural, absorption and luminescence characteristics of the samples provides evidence for two competing transition processes--quantum confinement induced widened band gap related transitions and oxide associated interface state mediated transitions. The results enable us to experimentally distinguish between the contributions of the two different transition mechanisms, which has hitherto been a challenging problem.     

Two- and three-photon absorption and frequency upconverted emission of silicon quantum dots

In this communication, we present the experimental results of two- and three-photon excitation studies on silicon quantum dots (QDs) in chloroform (as well as in water) by using femtosecond laser pulses with wavelengths of 778 and 1335 nm and a pulse duration approximately 160 fs. The photoluminescence spectral distributions are nearly the same upon one-, two-, and three-photon excitation. With one- and two-photon excitation, the temporal relaxation measurements of photoluminescence emission manifest the same multiexponential decay behavior in the time range from 0.05 ns to 15 mus, characterized by three successive decay constants: 0.75 ns, 300 ns, and 5 mus, respectively. Finally, the two-photon absorption spectrum in the spectral range of 650-900 nm and the three-photon absorption spectrum in the spectral range of 1150-1400 nm have been measured.     

CdS量子点的制备和光学性质

以醋酸镉、硫粉为原料制备CdS量子点,研究了硫的加入量对其光学性质的影响,结果表明:合成的CdS量子点粒径均匀,分散性较好,随着硫加入量的增加CdS量子点的粒径增大;反应中过量的硫能有效地填补硫空位,从而抑制表面态发光,同时,ODA的修饰也能有效地钝化表面态,减小表面态的发光强度.     

Identification and control of the origin of photoluminescence from silicon quantum dots

We present a detailed investigation into the origin of photoluminescence (PL) from silicon quantum dots in hydrogenated amorphous silicon nitride annealed in oxygen ambient. On the basis of structural characterization, temperature-dependent PL, time-resolved PL, and PL excitation spectra, we identify that the luminescence of the oxidized samples originates from the localized exciton radiative recombination via the surface states related to Si-N or Si-O-Si bonds. In combination with the results due to annealing in argon and hydrogen environments, we have further shown that control of the origin of the PL can be realized by modifying the radiative defect density through annealing treatment.     

Assessment of cytotoxicity of quantum dots and gold nanoparticles using cell-based impedance spectroscopy

A continuous online technique based on electric cell-substrate impedance sensing (ECIS) was demonstrated for measuring the concentration and time response function of fibroblastic V79 cells exposed to nanomaterials such as quantum dots (QDs) and fluorescent gold nanoparticles. The half-inhibition concentration, (ECIS50), the required concentration to attain 50% inhibition of the cytotoxic response, was estimated from the response function to ascertain cytotoxicity during the course of measurement. The ECIS50 values agreed well with the results obtained using the standard neutral red assay. Cadmium selenide quantum dots showed direct cytotoxicity with the ECIS assay. For the cadmium telluride quantum dots, significant toxicity could be assigned to free cadmium, although additional toxicity could be attributed to the QDs per se. The QDs synthesized with indium gallium phosphide and the fluorescent gold nanoparticles were not cytotoxic.     

Nanostructure assembly of indium sulphide quantum dots and their characterization

Nanocrystals (approximately 5 nm) of the semiconducting wide band gap material beta-In2S3 obtained by chemical synthesis through a hydrothermal route were characterized for phase and compositional purity. These nanoparticles exhibited quantum confinement characteristics as revealed by a blue-shifted optical absorption. These quantum dots of beta-In2S3 were electrically driven from a monodisperse colloidal suspension on to conducting glass substrates by Electophoretic Deposition (EPD) technique and nanostructural thin films were obtained. The crystalline and morphological structures of these deposits were investigated by X-ray diffraction and nanoscopic techniques. We report here that certain interesting nanostructural morphologies were observed in the two-dimensional quantum dot assemblies of beta-In2S3. The effect of the controlling parameters on the cluster growth and deposit integrity was also systematically studied through a series of experiments and the results are reported here.     

高质量水溶性CdTe量子点的合成与表征

以CdCl2和TeO2为原料,硼氢化钠为还原剂,采用水相合成法制备巯基丁二酸稳定CdTe量子点。研究了反应时间、碲和镉的物质的量之比等实验条件对CdTe量子点发光性能的影响,并用X射线粉末衍射、透射电镜、红外光谱、紫外-可见吸收光谱和荧光光谱等分析技术对其进行表征。实验表明,合成的量子点为立方晶型,颗粒大小分布均匀。反应时间及碲和镉的物质的量之比对量子点的发光性能有明显影响,随着反应时间的延长,量子点的吸收与荧光光谱都向长波方向移动,在pH值为10.5的碱性条件下,当n(Cd)∶n(Te)∶n(MSA)=1∶0.05∶1.4时,在5h的时间内可获得发绿色到红色荧光的量子点,最高荧光量子产率为70.3%。     

Wet route to silicon oxide quantum dots with fixed and strong blue emission

Amorphous silicon oxide quantum dots, with a quantum yield of 0.47 and blue emission fixed at 2.85 eV (433 nm), were obtained via two wet steps: first silicon nanowires reacted with potassium hydroxide at 50 °C, and then the resultants were kept in the dark and exposed to air at 20 °C. The silicon nanowires were synthesized in a high-temperature tube furnace using quartz powder and hydrogen as starting materials, and these products had less oxide outer cover and were ready to react with potassium hydroxide. The transmission electron microscopy was employed in order to characterize the amorphous quantum dots of silicon oxide.     

Green-emissive carbon quantum dots with high fluorescence quantum yield: Preparation and cell imaging

High fluorescence quantum yield (QY), excellent fluorescence stability, and low toxicity are essential for a good cellular imaging fluorescent probe. Green-emissive carbon quantum dots (CQDs) with many advantages, such as unique fluorescence properties, anti-photobleaching, low toxicity, fine biocompatibility and high penetration depth in tissues, have been considered as a potential candidate in cell imaging fluorescent probes. Herein, N, S-codoped green-emissive CQDs (QY= 64.03%) were synthesized by the one-step hydrothermal method, with m-phenylenediamine as the carbon and nitrogen source, and L-cysteine as the nitrogen and sulfur dopant, under the optimum condition of 200 °C reaction for 2 h. Their luminescence was found to originate from the surface state. In light of the satisfactory photobleaching resistance and the low cytotoxicity, CQDs were used as a cell imaging probe for HeLa cell imaging. The results clearly indicate that cells can be labeled with CQDs, which can not only enter the cytoplasm, but also enter the nucleus through the nuclear pore, showing their broad application prospect in the field of cell imaging.     

MBE grown InGaN quantum dots and quantum wells: effects of in-plane localization

InGaN/GaN heterostructure samples were grown by molecular beam epitaxy using ammonia as a nitrogen precursor. The growth of InGaN/GaN self-assembled quantum dots was monitored in situ by reflection high energy electron diffraction intensity oscillations. Atomic force microscopy scans showed a very high density of InGaN islands, 1×10¹¹ cm⁻², well above the dislocation density. This could explain the increased radiative efficiency of these samples compared to homogeneous quantum wells. Light emitting diodes (LEDs) with InGaN active layers buried in GaN were realized. Electroluminescence and photocurrent spectra of these LEDs evidence a strong Stokes shift that can be attributed to high localization of carriers in InGaN layers.