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Coherent spectroscopy of optically gated charged single InGaAs quantum dots.

The excited states of neutral and charged single InGaAs/GaAs quantum dots are studied using a confocal microspectroscopy technique. Because of their different Coulomb energy shifts, the charged and neutral states of the same quantum dot can be selectively excited. The charge of the quantum dot is controlled by a photo-depletion mechanism. Time-resolved coherent spectroscopy shows that the dephasing time of the excited states is longer when the quantum dot is charged. Rabi oscillation of the excited state of a singly charged quantum dot is demonstrated.

Journal Article↗

A self-assembled quantum dot probe for detecting beta-lactamase activity.

This communication describes a quantum dot probe that can be activated by a reporter enzyme, beta-lactamase. Our design is based on the principle of fluorescence resonance energy transfer (FRET). A biotinylated beta-lactamase substrate was labeled with a carbocyanine dye, Cy5, and immobilized on the surface of quantum dots through the binding of biotin to streptavidin pre-coated on the quantum dots. In assembling this nanoprobe, we have found that both the distance between substrates and the quantum dot surface, and the density of substrates are important for its function. The fluorescence emission from quantum dots can be efficiently quenched (up to 95%) by Cy5 due to FRET. Our final quantum dot probe, assembled with QD605 and 1:1 mixture of biotin and a Cy5-labeled lactam, can be activated by 32microg/mL of beta-lactamase with 4-fold increase in the fluorescence emission.

Fluorescence Resonance Energy Transfer↗

pH-sensitive ligand for luminescent quantum dots.

We developed a strategy to switch the luminescence of semiconductor quantum dots with chemical stimulations. It is based on the photoinduced transfer of either energy from CdSe-ZnS core-shell quantum dots to [1,3]oxazine ligands or electrons from the organic to the inorganic components. The organic ligands incorporate a dithiolane anchoring group, an electron-rich indole, and a 4-nitrophenylazophenoxy chromophore in their molecular skeleton. Their adsorption on the surface of the quantum dots results in partial luminescence quenching. Electron transfer from the indole fragment to the nanoparticles is mainly responsible for the decrease in luminescence intensity. Upon addition of base, the [1,3]oxazine ring of the ligands opens to generate a 4-nitrophenylazophenolate chromophore, which absorbs in the range of wavelengths where the quantum dots emit. This transformation activates an energy-transfer pathway from the excited nanoparticles to the ligands. In addition, the oxidation potential of the ligand shifts in the negative direction, improving the efficiency of electron transfer. The overall result is a decrease in the luminescence quantum yield of 83%. Addition of acid also opens the [1,3]oxazine ring of the ligands. However, the resulting 4-nitrophenylazophenol does not absorb in the visible region and cannot accept energy from the excited nanoparticles. Furthermore, the oxidation potential shifts in the positive direction, lowering the electron-transfer efficiency. In fact, the luminescence quantum yield increases by 33% as a result of this transformation. These changes are fully reversible and can be exploited to probe the pH of aqueous solutions from 3 to 11. Indeed, our sensitive quantum dots adjust their luminescence in response to variations in pH within this particular range of values. Thus, our general design strategy can eventually lead to the development of pH-sensitive luminescent probes for biomedical applications based on the unique photophysical properties of semiconductor quantum dots.

Journal Article↗

Size-dependent fine-structure splitting in self-organized InAs/GaAs quantum dots.

A systematic variation of the exciton fine-structure splitting with quantum dot size in single quantum dots grown by metal-organic chemical vapor deposition is observed. The splitting increases from to as much as with quantum dot size. A change of sign is reported for small quantum dots. Model calculations within the framework of eight-band theory and the configuration interaction method were performed. Different sources for the fine-structure splitting are discussed, and piezoelectricity is pinpointed as the only effect reproducing the observed trend.

Journal Article↗

Teleportation on a quantum dot array.

We present a model of quantum teleportation protocol based on a double quantum dot array. The unknown qubit is encoded using a pair of quantum dots, with one excess electron, coupled by tunneling. It is shown how to create a maximally entangled state using an adiabatically increasing Coulomb repulsion between different dot pairs. This entangled state is exploited to perform teleportation again using an adiabatic coupling between itself and the incoming unknown state. Finally, a sudden separation of Bob's qubit allows a time evolution of Alice's, which amounts to a modified version of standard Bell measurement. A transmission over a long distance could be obtained by considering the entangled state of a chain of N coupled double quantum dots. The system is shown to be increasingly robust with N against decoherence due to phonons.

Journal Article↗

Quantum dots with a paramagnetic coating as a bimodal molecular imaging probe.

MRI detectable and targeted quantum dots were developed. To that aim, quantum dots were coated with paramagnetic and pegylated lipids, which resulted in a relaxivity, r(1), of nearly 2000 mM(-1)s(-1) per quantum dot. The quantum dots were functionalized by covalently linking alphavbeta3-specific RGD peptides, and the specificity was assessed and confirmed on cultured endothelial cells. The bimodal character, the high relaxivity, and the specificity of this nanoparticulate probe make it an excellent contrast agent for molecular imaging purposes.

Cells, Cultured↗

Engineering luminescent quantum dots for in vivo molecular and cellular imaging.

Semiconductor quantum dots are luminescent nanoparticles that are under intensive development for use as a new class of optical imaging contrast agents. Their novel properties such as optical tunability, improved photostability, and multicolor light emission have opened new opportunities for imaging living cells and in vivo animal models at unprecedented sensitivity and spatial resolution. Combined with biomolecular engineering strategies for tailoring the particle surfaces at the molecular level, bio-conjugated quantum dot probes are well suited for imaging single-molecule dynamics in living cells, for monitoring protein-protein interactions within specific intracellular locations, and for detecting diseased sites and organs in deep tissue. In this article, we describe the engineering principles for preparing high-quality quantum dots and for conjugating the dots to biomolecular ligands. We also discuss recent advances in using quantum dots for in vivo molecular and cellular imaging.

Animals↗

Imaging a single-electron quantum dot.

Images of a single-electron quantum dot were obtained in the Coulomb blockade regime at liquid He temperatures using a cooled scanning probe microscope (SPM). The charged SPM tip shifts the lowest energy level in the dot and creates a ring in the image corresponding to a peak in the Coulomb-blockade conductance. Fits to the line shape of the ring determine the tip-induced shift of the energy of the electron state in the dot. SPM manipulation of electrons in quantum dots promises to be useful in understanding, building, and manipulating circuits for quantum information processing.

Arsenicals↗

Reduction in nonfluorescence state of quantum dots on an immunofluorescence staining.

Fluorescence quantum dots are widely used in immunofluorescence staining because of their intense and stable fluorescence. However, the nonfluorescence state of the quantum dots is their disadvantage. Here, the nonfluorescence state of the dots labeled to cells and tissues was suppressed. Cells and tissues where the receptor HER2 had been overexpressed were fixed and then labeled with anti-HER2 crosslinked with the dots. The intensity of the dots increased with the illumination time. The majority of the single dots were in the nonfluorescence state at beginning of the illumination period and the number of fluorescence dots observed increased with the illumination time. Living cells were also labeled with the anti-HER2-Qdots. Blinking and bleaching of the Qdots was effectively suppressed by adding beta-mercaptoethanol and glutathione. Therefore, the movement of the Qdots bound to cell membrane could be observed for long periods of time.

Animals↗

Side chain mediated electronic contact between a tetrahydro-4H-thiopyran-4-ylidene-appended polythiophene and CdTe quantum dots.

The properties of a mixed CdTe quantum dot/tetrahydro-4H-thiopyran-4-ylidene-functionalized polythiophene system are reported. This system was prepared by exposing trioctylphosphine (TOP)-capped CdTe quantum dots to the polythiophene in solution. Strong fluorescence emission quenching and shortening of the fluorescence emission lifetimes of both the polythiophene and the quantum dots occur when they are mixed, indicating the occurrence of photoinduced charge separation. Photoinduced absorption spectroscopy reveals a considerable decrease in the population of the polythiophene triplet excited state in the mixed system. These results demonstrate that between the quantum dots and the polythiophene there is both physical and electronic contact, which is mediated by the tetrahydro-4H-thiopyran-4-ylidene side chains.

Journal Article↗

Development and application of quantum dots for immunocytochemistry of human erythrocytes.

Recent developments in quantum dot technology have resulted in the introduction of new fluorescence immunocytochemical probes. In contrast to organic fluorophores, which are not photostable, the high quantum yield and remarkable photostability of quantum dots solve major problems associated with immunocytochemical studies of erythrocytes. We report here the first application of quantum dots to immunocytochemical studies of human erythrocytes capable of being used in high-magnification, three-dimensional erythrocyte reconstruction techniques. The procedure consists of stabilizing human erythrocytes with a homofunctional imidoester cross-linker to minimize fixative-induced autofluorescence followed by reacting with a quantum dot - monoclonal antibody complex to label band 3 protein. Our new procedure clearly showed a non-homogeneous, raft-like distribution of band 3 protein in the erythrocyte membrane. We also demonstrate the applicability of our technique to studies of erythrocyte membrane modifications occurring during the invasion of a malaria parasite.

Animals↗

Vacuum Rabi splitting with a single quantum dot in a photonic crystal nanocavity.

Cavity quantum electrodynamics (QED) systems allow the study of a variety of fundamental quantum-optics phenomena, such as entanglement, quantum decoherence and the quantum-classical boundary. Such systems also provide test beds for quantum information science. Nearly all strongly coupled cavity QED experiments have used a single atom in a high-quality-factor (high-Q) cavity. Here we report the experimental realization of a strongly coupled system in the solid state: a single quantum dot embedded in the spacer of a nanocavity, showing vacuum-field Rabi splitting exceeding the decoherence linewidths of both the nanocavity and the quantum dot. This requires a small-volume cavity and an atomic-like two-level system. The photonic crystal slab nanocavity--which traps photons when a defect is introduced inside the two-dimensional photonic bandgap by leaving out one or more holes--has both high Q and small modal volume V, as required for strong light-matter interactions. The quantum dot has two discrete energy levels with a transition dipole moment much larger than that of an atom, and it is fixed in the nanocavity during growth.

Journal Article↗

A new bioimaging carrier for fluorescent quantum dots: phospholipid nanoemulsion mimicking natural lipoprotein core.

Fluorescent quantum dots (semiconductor nanocrystals) have the potential to revolutionize biological imaging, but their use has been limited by difficulties in obtaining quantum dots that are water soluble and biocompatible. The objectives of our research were to develop a methodology for encapsulation of cadnium-selenium (CdSe) quantum dots (QDs) in phospholipid nanoemulsion that mimics the natural lipoprotein core and to study their interactions with cultured non-small cell lung cancer cells (NSCLC). We found that CdSe QDs can be efficiently encapsulated in the phospholipid nanoemulsion. The QD nanoemulsion has a particle size approximately 80 nm and appears physically stable. The QD nanoemulsion interacts well with cells. The intensity of cellular fluorescence imaging increases with the cell incubation time, indicating more QDs were taken up by the cells, respectively. Two types of fluorescence microscopies confirm that QDs are primarily localized in the cytoplasm but not in the nucleus of the cells.

Cadmium Compounds↗

Probing lectin and sperm with carbohydrate-modified quantum dots.

We report the encapsulation of quantum dots with biologically important beta-N-acetylglucosamine (GlcNAc) in different ratios, together with studies of their specific/sensitive multivalent interactions with lectins and sperm by fluorimetry, transmission electron microscopy, dynamic light scattering microscopy, confocal imaging techniques, and flow cytometry. These GlcNAc-encapsulated quantum dots (QDGLNs) specifically bind to wheat germ agglutinin, and cause fluorescence quenching and aggregation. Further studies of QDGLNs and the mannose-encapsulated QDs (QDMANs) with sperm revealed site-specific interactions, in which QDGLNs bind to the head of the sperm, while QDMANs spread over the whole sperm body.

Acetylglucosamine↗

[Study of water-sol core-shell CdSe/CdS quantum dots].

Water-sol core/shell CdSe/CdS quantum dots (QDs) were synthesized in aqueous solution by using mercapto-acetate acid as stabilizer. The UV-Vis absorption and emission spectra were studied. The size of the SdSe-core was about 2 nm estimated by absorption edge and X-ray powder diffraction(XRD). The structure was also characterized by X-ray photoelectron spectroscopy(XPS). The intensity of luminescence of the quantum dots was greatly enhanced after the surface was modified with CdS shell. Red shift of the peak was shown in both the emission and absorption spectra.

Algorithms↗

Rabi oscillations of excitons in single quantum dots.

Transient nonlinear optical spectroscopy, performed on excitons confined to single GaAs quantum dots, shows oscillations that are analogous to Rabi oscillations in two-level atomic systems. This demonstration corresponds to a one-qubit rotation in a single quantum dot which is important for proposals using quantum dot excitons for quantum computing. The dipole moment inferred from the data is consistent with that directly obtained from linear absorption studies. The measurement extends the artificial atom model of quantum dot excitonic transitions into the strong-field limit, and makes possible full coherent optical control of the quantum state of single excitons using optical pi pulses.

Journal Article↗

Universal polyethylene glycol linkers for attaching receptor ligands to quantum dots.

Biologically active small molecule derivatives that can be conjugated to quantum dots have the promise of revolutionizing fluorescent imaging in biology. In order to achieve this several technical hurdles have to be surmounted, one of which is non-specific adsorption of quantum dots to cell membranes. Pegylating quantum dots has been shown to eliminate non-specific binding. Consequently it is necessary to develop a universal synthetic methodology to attach small molecule ligands to polyethylene glycol. These pegylated small molecules may then be conjugated to the surfaces of quantum dots. Ideally this universal strategy should be adaptable and be applicable to PEG chains of varying lengths. This paper describes the development of one such methodology and the synthesis of a pegylated derivative of the known 5HT(2) agonist 1-(2-aminopropyl)-2,5-dimethoxy benzene. This compound was tested and found to be an agonist for the 5HT(2A) and 5HT(2C) receptor having EC(50) values of 250 and 50 nM, respectively.

Cell Membrane↗