Assembly Of Quantum Dots Research Articles

CdS/MoS2 heterojunction-based photoelectrochemical DNA biosensor via enhanced chemiluminescence excitation.

This work developed a CdS/MoS2 heterojunction-based photoelectrochemical biosensor for sensitive detection of DNA under the enhanced chemiluminescence excitation of luminol catalyzed by hemin-DNA complex. The CdS/MoS2 photocathode was prepared by the stepwise assembly of MoS2 and CdS quantum dots (QDs) on indium tin oxide (ITO), and achieved about 280% increasing of photocurrent compared to pure CdS QDs electrode due to the formation of heterostructure. High photoconversion efficiency in the photoelectrochemical system was identified to be the rapid spatial charge separation of electron-hole pairs by the extension of electron transport time and electron lifetime. In the presence of target DNA, the catalytic hairpin assembly was triggered, and simultaneously the dual hemin-labeled DNA probe was introduced to capture DNA/CdS/MoS2 modified ITO electrode. Thus the chemiluminescence emission of luminol was enhanced via hemin-induced mimetic catalysis, leading to the physical light-free photoelectrochemical strategy. Under optimized conditions, the resulting photoelectrode was proportional to the logarithm of target DNA concentration in the range from 1 fM to 100 pM with a detection limit of 0.39 fM. Moreover, the cascade amplification biosensor demonstrated high selectivity, desirable stability and good reproducibility, showing great prospect in molecular diagnosis and bioanalysis.

Highly Sensitive Electrochemical Determination of Alfatoxin B1 Using Quantum Dots-Assembled Amplification Labels.

A competitive electrochemical immunoassay for highly sensitive detection of AFB1 is demonstrated using layer-by-layer (LBL) assembled quantum dots (QDs) as labels. To investigate the effects of the higher sensitivity of square wave voltammetric stripping (SWV) and of the LBL technique on the proposed immunoassays, the proposed assay was compared to electrochemical (EC) and fluorescent immunoassays, which did not use LBL technology. Peanut samples were analyzed using the three immunoassays. The limits of detection (LODs) were 0.018, 0.046 and 0.212 ng/mL, respectively, while the sensitivities were 0.308, 1.011 and 4.594 ng/mL, respectively. The proposed electrochemical immunoassay displayed a significant improvement in sensitivity, thereby providing a simple and sensitive alternative strategy for determining AFB1 levels in peanut samples.

Micelle-Encapsulated Quantum Dot-Porphyrin Assemblies as in Vivo Two-Photon Oxygen Sensors.

Micelles have been employed to encapsulate the supramolecular assembly of quantum dots with palladium(II) porphyrins for the quantification of O2 levels in aqueous media and in vivo. Förster resonance energy transfer from the quantum dot (QD) to the palladium porphyrin provides a means for signal transduction under both one- and two-photon excitation. The palladium porphyrins are sensitive to O2 concentrations in the range of 0-160 Torr. The micelle-encapsulated QD-porphyrin assemblies have been employed for in vivo multiphoton imaging and lifetime-based oxygen measurements in mice with chronic dorsal skinfold chambers or cranial windows. Our results establish the utility of the QD-micelle approach for in vivo biological sensing applications.

Quantum Dot/Liquid Crystal Nanocomposites in Photonic Devices

Quantum dot/liquid crystal nano-composites are promising new materials for a variety of applications in energy harvesting, displays and photonics including the liquid crystal laser. To realize many applications, however, we need to control and stabilize nano-particle dispersion in different liquid crystal host phases and understand how the particles behave in an anisotropic fluid. An ideal system will allow for the controlled assembly of either well-defined nano-particle clusters or a uniform particle distribution. In this paper, we investigate mesogen-functionalized quantum dots for dispersion in cholesteric liquid crystal. These nanoparticles are known to assemble into dense stable packings in the nematic phase, and such structures, when localized in the liquid crystal defects, can potentially enhance the coupling between particles and a cholesteric cavity. Controlling the dispersion and assembly of quantum dots using mesogenic surface ligands, we demonstrate how resonant fluid photonic cavities can result from the co-assembly of luminescent nanoparticles in the presence of cholesteric liquid crystalline ordering.

Synthesis of Porphyrin-CdSe Quantum Dot Assemblies: Controlling Ligand Binding by Substituent Effects.

Cadmium selenide quantum dots of 2.2-2.3 nm diameter were prepared by phosphorus-free methods using oleic acid as stabilizing surface ligand. Ligand exchange monitored quantitatively by (1)H NMR spectroscopy gave an estimate of 30-38 monodentate ligands per nanocrystal, with a ligand density of 1.8-2.3 nm(-2). The extent of ligand exchange with macrocycles carrying one or more functional groups was investigated, with the aim of producing nanocrystal-macrocycle conjugates with a limited number of coligands. Metal-free porphyrins are able to sequester the Cd(2+) ions from the Cd(oleate)2 outer layer of the nanocrystals. Zinc porphyrin complexes carrying one carboxylate function displace oleate efficiently to give porphyrin/CdSe composites with porphyrins stacked upright on the crystal surface. Porphyrins with four potential ligating sites are able to bind to the crystal surface only if the donors are at the end of sufficiently long and flexible tethers. High-dilution methods allowed the synthesis and isolation of well-defined composites of composition [CdSe{porphyrin}2], where porphyrin = 5,10,15,20-tetrakis{3-(carboxy-n-alkyloxy)phenyl}porphyrinato zinc (n = 5 or 10) and 5,10,15,20-tetrakis{3-(11-undecenyloxythiol)phenyl}porphyrinato zinc. Comparison of the composition data obtained by (1)H NMR spectroscopy with luminescence quenching behavior suggests a dependence of quenching efficiency on the tether length. Luminescence quenching was also observed for porphyrins that, according to (1)H NMR results, do not undergo surface ligand exchange.

Layer-by-Layer Assembly of Stable Aqueous Quantum Dots for Luminescent Planar Plate.

This work reports the fabrication of a luminescent planar plate based on stable aqueous quantum dots (QDs) and poly(diallyldimethylammonium chloride) (PDDA) via a layer-by-layer (LBL) assembly technique. Preparation of aqueous QDs with facile monoalkyl maleate amphiphilic surfactants as the coating agent is conducted by a robust and efficient phase-transfer method. The as-prepared aqueous QDs exhibit bright emission, and their surface has very large negative zeta potential values, which are useful for electrostatic LBL assembly. Red, green, and blue luminescent planar plates are successfully fabricated via LBL assembly of the monocolor QDs, respectively. Through accurately adjusting the relative proportion of each monocolor luminescent component, we obtain an inspiring luminescent planar plate, which emits bright white light with a color coordinate of (0.3509, 0.3483), a correlated color temperature (CCT) of 4766 K, and a high color rendering index (CRI, Ra) of 89.5 under the irradiation of UV light. Therefore, this paper reports a facile process for the design and preparation of luminescent planar plates, which have potential applications in display and solid-state lighting devices.

Tuning the tunneling probability between low-dimensional electron systems by momentum matching

We demonstrate the possibility to tune the tunneling probability between an array of self- assembled quantum dots and a two-dimensional electron gas (2DEG) by changing the energy imbalance between the dot states and the 2DEG. Contrary to the expectation from Fowler-Nordheim tunneling, the tunneling rate decreases with increasing injection energy. This can be explained by an increasing momentum mismatch between the dot states and the Fermi-circle in the 2DEG. Our findings demonstrate momentum matching as a useful mechanism (in addition to energy conservation, density of states, and transmission probability) to electrically control the charge transfer between quantum dots and an electron reservoir.

Assembly of CdS Quantum Dots onto Hierarchical TiO2 Structure for Quantum Dots Sensitized Solar Cell Applications

Quantum dot (QD) sensitized solar cells based on Hierarchical TiO2 structure (HTS) consisting of spherical nano-urchins on transparent conductive fluorine doped tin oxide glass substrate is fabricated. The hierarchical TiO2 structure consisting of spherical nano-urchins on transparent conductive fluorine doped tin oxide glass substrate synthesized by hydrothermal route. The CdS quantum dots were grown by the successive ionic layer adsorption and reaction deposition method. The quantum dot sensitized solar cell based on the hierarchical TiO2 structure shows a current density JSC = 1.44 mA, VOC = 0.46 V, FF = 0.42 and η = 0.27%. The QD provide a high surface area and nano-urchins offer a highway for fast charge collection and multiple scattering centers within the photoelectrode.

Charge carrier transport through 3D assemblies of zincblende CdSe and ZnSe quantum dots in weak size-quantization regime

The mechanism of charge carrier transport through 3D assemblies of ZnSe and CdSe quantum dots with zincblende structure in weak size-quantization regime was investigated. The Debye length in the case of ZnSe QDs was found to be 11.5 nm, i.e. almost three times larger than the average diameter of the nanocrystals constituting the films annealed at 250 °C. In CdSe QDs, on the other hand, the Debye’s length of 11.8 nm was almost twice smaller than the average crystal diameter in the films annealed at 300 °C. In the case of ZnSe QD assemblies, it was found that the predominant mechanism governing the charge carrier transport in temperature range from 380 to 650 K is the thermionic emission, with the trap levels taking part in the formation of crystal boundary barrier being located above the Fermi level. Combining temperature-dependent conductivity data with the data from optical absorption studies, the actual position of the trap level was estimated to be at about 0.37 eV (referred to the intrinsic Fermi level at the interface). In contrast to the case of ZnSe, the temperature dependence of conductivity in the case of thin films composed by 3D assemblies of CdSe QDs appeared to be much more complex. In the highest temperature region in which the temperature-dependent conductivity measurements were performed for this system (from 480 to 540 K), it was found that the thermally activated band-to-band electronic transitions govern the conductivity changes, the corresponding thermal band gap energy being 1.85 eV. In the lower-temperature region, down to 300 K, the thermionic emission was found to be predominant charge carrier transport mechanism, with trap levels being positioned above the Fermi level. The two detected trap levels were found to be located at 0.46 and 0.79 eV, corresponding to the measured conductivity activation energies of 0.84 and 0.51 eV.

Phosphorylation-directed assembly of a single quantum dot based nanosensor for protein kinase assay.

Protein kinases play crucial roles in intracellular signal transduction and metabolic pathways, and the monitoring of protein kinase activity is essential to the understanding of fundamental biochemical processes and the clinical diagnosis. Here, we demonstrate the phosphorylation-directed assembly of a single quantum dot (QD)-based nanosensor for sensitive detection of cAMP-dependent protein kinase (PKA). This assay involves (1) the PKA-directed simultaneous phosphorylation and biotinylation of cyanine 5 (Cy5)-labeled substrate peptides, (2) the assembly of phosphorylated and biotinylated peptides onto the surface of the QD, and (3) the illumination of Cy5 by means of fluorescence resonance energy transfer (FRET) between the QD and Cy5. With an adenosine triphosphate (ATP) analogue, γ-biotin-ATP, as the phosphoryl donor, the PKA-catalyzed phosphorylation reaction incorporates the biotin-conjugated phosphate group into the substrate peptides to form the biotinylated peptides. The biotin entity subsequently drives the assembly of peptides onto the surface of streptavidin-functionalized QD to form the sandwiched Cy5-peptide-QD nanostructure, enabling the occurrence of FRET between the QD and Cy5. The FRET signal can be easily recorded by either the conventional fluorescence spectrometer or the total internal reflection fluorescence (TIRF) microscope. In contrast, the absence of PKA cannot lead to the formation of Cy5-peptide-QD complex and no Cy5 signal can be detected. This protein kinase-actuated FRET assay is straightforward, without the involvement of either washing or separation steps, and has a significant advantage of high sensitivity with a detection limit of 9.3 × 10(-6) U/μL. Moreover, this method can be used to estimate the half-maximal inhibitory concentration (IC50) value of PKA inhibitor H-89 (N-[2-(p-bromocinnamylamino)ethyl]-5-isoquinolinesulfonamide dihydrochloride) and to monitor forskolin (Fsk)/3-isobutyl-1-methylxanthine (IBMX)-triggered activation of PKA in cell lysates, thus holding great potential for further applications in protein kinase-related biological researches and drug discovery.

23pPSA-31 高密度CuCl量子ドット集合系における励起子分子超蛍光の温度依存性

23pPSA-31 高密度CuCl量子ドット集合系における励起子分子超蛍光の温度依存性

Selective room temperature phosphorescence detection of heparin based on manganese-doped zinc sulfide quantum dots/polybrene self-assembled nanosensor

A selective system was developed to detect heparin in aqueous solutions by using MPA(3-Mercaptopropionic Acid)-capped Mn-doped ZnS quantum dots (QDs)/polybrene (hexadimethrine bromide) hybrids as a sensitive room temperature phosphorescence (RTP) nanosensor. In this system, the RTP intensity of QDs was remarkably enhanced via electrostatic self-assembly after the addition of polybrene. The addition of heparin into the system was competitively bound to polybrene and enable to deprive it from the surface of QDs, as a result, the RTP intensity of Mn-doped ZnS QDs/polybrene hybrids was reduced with the increased of heparin concentration. Based on this effect, a selective system was proposed to detect heparin. Under the optimal conditions, the change of RTP intensity was proportional to the heparin concentration from 0.05 to 1.4UmL−1 (about 0.38–10.76μgmL−1) and the limit of detection (LOD) was 0.021UmL−1 (about 0.16μgmL−1). This proposed nanosensor is simple and relatively free of interference from coexisting substances, which can be applied to detect heparin in heparin injection and human serum. In addition, a new pathway was also provided based on the assembly of QDs with other cationic homopolymers for further design of biosensors and detection of biomolecules.

Ultrasensitive atomic fluorescence spectrometric detection of DNA with quantum dot-assemblies as signal amplification labels

Using self-assembled CdS QDs as signal amplification labels, an ultrasensitive AFS method was bridged to DNA detection, with an impressive limit of detection of 0.8 aM.

Assembly of a CdS quantum dot–TiO2 nanobelt heterostructure for photocatalytic application: towards an efficient visible light photocatalyst via facile surface charge tuning

CdS QD sensitized TiO2 nanobelt nanostructures were fabricated by a facile self-assembly approach and the photocatalytic performance of the well-defined hybrid heterostructure was systematically probed.

Sulfur-doped graphitic carbon nitride decorated with graphene quantum dots for an efficient metal-free electrocatalyst

A rational assembly of graphene quantum dots in situ decorated onto sulfur-doped graphitic carbon nitride nanosheets for an efficient electrocatalyst.

Electrically driven assembly of CdTe quantum dots into photoconductive microwires

Low energy, low cost quantum dot nanocrystal assembly into one-dimensional microwires for optoelectronic device applications.

DNA mediated assembly of quantum dot–protoporphyrin IX FRET probes and the effect of FRET efficiency on ROS generation

Photodynamic therapy (PDT) involves generation of reactive oxygen species (ROS) by the irradiation of a photosensitizer. Controlled and targeted release of ROS by a photosensitizer is crucial in PDT. For achieving controlled generation of ROS, a ZnSe/ZnS quantum dot (QD) donor and protoporphyrin IX (Pp IX) acceptor based fluorescence resonance energy transfer (FRET) probe is reported here. The QDs and Pp IX are assembled either by direct conjugation or through DNA hybridization. Complementary DNA strands are individually conjugated to the QDs and Pp IX by amide coupling. Due to the overlap of the emission spectrum of QDs and the absorption spectrum of Pp IX, efficient transfer of energy from QDs to Pp IX was observed in both the cases. The FRET efficiency was quantitatively evaluated by steady-state and time-resolved spectroscopy and compared between the QD-Pp IX direct conjugate and QD-DNA-Pp IX assembly at various donor to acceptor ratios. Since a single QD can harbor a multiple number of Pp IX-DNA counterparts through DNA hybridization, the FRET efficiency was found to increase with the increase in the number of Pp IX acceptors. ROS generation from Pp IX was studied for the FRET pairs and was found to be affected by the irradiation time of the QD donor.

Plasmonics: Hybrid Graphene–Giant Nanocrystal Quantum Dot Assemblies with Highly Efficient Biexciton Emission (Advanced Optical Materials 1/2015)

When giant nanocrystal quantum dots (g-NQDs) are coupled to graphene, pairs of excitons optically excited in the g-NQDs experience efficient recombination and subsequent simultaneous emission of photon pairs. This enhancement is provided by a localized plasmon supported by a charge puddle that forms underneath the photocharged g-NQD. On page 39, H. Htoon and co-workers reveal the tremendous potential of graphene-g-NQD hybrids for lasing and entangled photon source applications.

(In,Mn)As multilayer quantum dot structures

(In,Mn)As multilayer quantum dots structures were grown by molecular beam epitaxy using a Mn selective doping of the central parts of quantum dots. The study of the structural and magneto-optical properties of the samples with three and five layers of (In,Mn)As quantum dots has shown that during the quantum dots assembly, the out-diffusion of Mn from the layers with (In,Mn)As quantum dots can occur resulting in the formation of the extended defects. To produce a high quality structures using the elaborated technique of selective doping, the number of (In,Mn)As quantum dot layers should not exceed three.

In situ generation of electron acceptor for photoelectrochemical biosensing via hemin-mediated catalytic reaction.

A novel photoelectrochemical sensing strategy is designed for DNA detection on the basis of in situ generation of an electron acceptor via the catalytic reaction of hemin toward H2O2. The photoelectrochemical platform was established by sequential assembly of near-infrared CdTe quantum dots, capture DNA, and a hemin-labeled DNA probe to form a triple-helix molecular beacon (THMB) structure on an indium tin oxide electrode. According to the highly catalytic capacity of hemin toward H2O2, a photoelectrochemical mechanism was then proposed, in which the electron acceptor of O2 was in situ-generated on the electrode surface, leading to the enhancement of the photocurrent response. The utilization of CdTe QDs can extend the absorption edge to the near-infrared band, resulting in an increase in the light-to-electricity efficiency. After introducing target DNA, the THMB structure is disassembled and releases hemin and, thus, quenches the photocurrent. Under optimized conditions, this biosensor shows high sensitivity with a linear range from 1 to 1000 pM and detection limit of 0.8 pM. Moreover, it exhibits good performance of excellent selectivity, high stability, and acceptable fabrication reproducibility. This present strategy opens an alternative avenue for photoelectrochemical signal transduction and expands the applications of hemin-based materials in photoelectrochemical biosensing and clinical diagnosis.