Infra red quantum dot photolithography

CdS quantum dots were fabricated photolithographically on the surface and in the bulk of silica hydrogels, as well as on the surface of planar substrates. Silica hydrogels were prepared with a standard base-catalyzed route, and the solvent was exchanged with a cold aqueous solution of Cd(NO₃)₂, NH₄OH, thiourea, and a capping agent, e.g., 2-mercaptoethanol. The samples were then exposed to a focused infrared beam produced by a continuous-wave Nd:YAG laser. The precursors reacted upon heating, and CdS nanoparticles formed in the illuminated regions. Use of capping agents allowed to control the mean particle size, while focusing of the beam inside hydrogel monoliths generated nanoparticles in their bulk, but not at the surface. Planar substrates were patterned by illuminating a precursor solution spin-coated on the substrates. The average size of the CdS nanoparticles could be varied between about 1.5 and 4.5 nm by varying the type and the concentration of the capping agents.     

Organized quantum dot array through nanochemistry

Well defined tetrahedral cadmium sulfide nanocrystals were made in a rational way by organometallic chemical synthesis. Due to the fair degree of the ionic character in Cd—S bond, the sulfide S^2– can be replaced by the organothiolate RS^– without disrupting the CdS lattice structure. These ligands were delicately chosen to fabricate anisotropically capped nanocrystals. During solvent evaporation, these smart dots have the property to self-connect in a head-to-tail alignment leading to a new fibrous polymeric dot material. These quantum microcrystallites can be processed to make powder, free standing dots or optically transparent and anisotropic films. Optical spectroscopy, X-ray diffraction and electron microscopy have been used to characterize this organized quantum dot array.     

Some aspects of quantum dot toxicity

Quantum dot toxicity has become a hot topic in recent years due to the emergence of semiconductor nanoparticles as highly efficient biological imaging agents. The use of quantum dots in biology is arguably the most successful application of pure nanotechnology in recent times, although unfortunately, the most useful semiconductor particles contain elements that are often thought to be detrimental to health and the environment. In this article, we explore some key reports on this issue.     

Metal-peptide nanoassemblies

A new class of metal-peptide nanoassemblies has been prepared by combining the principles of supramolecular coordination chemistry with those of de novo protein design.     

Impact dynamics of colloidal quantum dot solids

We use aerosol techniques to investigate the cohesive and granular properties of solids composed of colloidal semiconductor nanocrystals (quantum dot solids). We form spherical agglomerates of nanocrystals with a nebulizer and direct them toward a carbon substrate at low (~0.01 m/s) or high (~100 m/s) velocities. We then study the morphology of the deposit (i.e., the "splat") after impact. By varying the size of the agglomerate and the spacing between the nanocrystals within it, we observe influences on the mechanical properties of the quantum dot solid. We observe a liquid-to-solid transition as the nanocrystals become more densely packed. Agglomerates with weakly interacting nanocrystals exhibit liquidlike splashing and coalescence of overlapping splats. More dense agglomerates exhibit arching and thickening effects, which is behavior typical of granular materials.     

Tuning electrochemical rectification via quantum dot assemblies

A novel approach to tuning electrochemical rectification using 2D assemblies of quantum dots (QDs) is presented. Asymmetric enhancement of the oxidation and reduction currents in the presence of the Fe(CN)(6)(3-/4-) redox couple is observed upon adsorption of QDs at thiol-modified Au electrodes. The extent of the electrochemical rectification is dependent on the average QD size. A molecular blocking layer is generated by self-assembling 11-mercaptoundecanoic acid (MUA) and an ultrathin film of poly(diallyldimethylammonium chloride) (PDADMAC) on the electrode. The polycationic film allows the electrostatic adsorption of 3-mercaptopropionic acid (MPA)-stabilized CdTe QDs, generating 2D assemblies with approximately 0.4% coverage. The QD adsorption activates a fast charge transfer across the blocking layer in which the reduction process is more strongly enhanced than the oxidation reaction. The partial electrochemical rectification is rationalized in terms of the relative position of the valence (VB) and conduction band (CB) edges with respect to the redox Fermi energy (ε(redox)). Quantitative analysis of the exchange current density obtained from electrochemical impedance spectroscopy demonstrates that the enhancement of charge transport across the molecular barrier is strongly dependent on the position of the QD valence band edge relative to ε(redox). The average electron tunneling rate constant through the QD assemblies is estimated on the basis of the Gerischer model for electron transfer.     

Layer-by-layer quantum dot constructs using self-assembly methods

We describe the creation of CdSe/ZnS quantum dot assemblies using layer-by-layer construction strategies, using self-assembly. In the first approach, a dithiol linker was used to make multilayers of CdSe/ZnS quantum dots, while in the second biotin- and streptavidin-conjugated CdSe/ZnS quantum dots were used to make multilayer constructs. Both the chemical bonding nature and fluorescence spectroscopic properties of quantum dot films were characterized using X-ray photoelectron spectroscopy (XPS) and fluorescence spectroscopy.     

Nanostructured thermoresponsive quantum dot/PNIPAM assemblies

Synthesis, characterization, and applications of novel thermoresponsive polymeric coatings for quantum dots (QDs) are presented. Comb-copolymers featuring hydrophobic alkyl groups, carboxylic groups and poly(N-isopropylacrylamide) (PNIPAM) side chains with molar masses ranging from 1000 g/mol to 25,400 g/mol were obtained. The amphiphilic comb-copolymers were shown to efficiently transfer the QDs to aqueous media. The PNIPAM-coated QD materials display a lower critical solution temperature (LCST). The absorbance, luminescence emission, size of the assemblies, and electrophoretic mobility were followed as a function of temperature and the reversibility of the temperature induced changes is demonstrated by cyclic heating and cooling.     

Temperature-sensitive photoluminescence of CdSe quantum dot clusters

The formation of narrow size dispersed and nanometer size aggregates (clusters) of cadmium selenide (CdSe) quantum dots (QDs) and their temperature-sensitive photoluminescence (PL) spectral properties close to room temperature (298 K) are discussed. CdSe QDs formed stable clusters with an average diameter of approximately 27 nm in the absence of coordinating solvents. Using transmission electron microscopy (TEM) imaging, we identified the association of individual QDs with 2-5 nm diameters into clusters of uniform size. A suspension of these clusters in different solvents exhibited reversible PL intensity changes and PL spectral shifts which were correlated with temperature. Although the PL intensity of CdSe QDs encapsulated in host matrixes and the solid state showed a response to temperature under cryogenic conditions, the current work identified for the first time QD clusters showing temperature-sensitive PL intensity variations and spectral shifts at moderate temperatures above room temperature. Temperature-sensitive reversible PL changes of clusters are discussed with respect to reversible thermal trapping of electrons at inter-QD interfaces and dipole-dipole interactions in clusters. Reversible luminescence intensity variations and spectral shifts of QD clusters show the potential for developing sensors based on QD nanoscale assemblies.     

Microfluidic generation of multifunctional quantum dot barcode particles

We develop a new strategy to prepare quantum dot (QD) barcode particles by polymerizing double-emulsion droplets prepared in capillary microfluidic devices. The resultant barcode particles are composed of stable QD-tagged core particles surrounded by hydrogel shells. These particles exhibit uniform spectral characteristics and excellent coding capability, as confirmed by photoluminescence analyses. By using double-emulsion droplets with two inner droplets of distinct phases as templates, we have also fabricated anisotropic magnetic barcode particles with two separate cores or with a Janus core. These particles enable optical encoding and magnetic separation, thus making them excellent functional barcode particles in biomedical applications.     

Patterning of quantum dot bioconjugates via particle lithography

We present a simple technique to fabricate hexagonally ordered quantum dot bioconjugate (QDBC) dot arrays on glass coverslips. We used particle lithography to create periodic holes in a layer of methoxy-poly(ethylene glycol)-silane and then adsorbed QDBCs into the holes. To demonstrate the versatility of this technique, we made separate periodic arrays of quantum dots (QDs) conjugated to three different biologically important molecules: biotin, streptavidin, and anti-mouse IgG. The diameters of the regions where the QDBCs adsorbed were 500-600 nm and independent of the QDBC patterned. The site density of the QDBCs in the patterned holes could be varied by simply adjusting the coating concentration of the QDBC solution. We demonstrate the applicability of these substrates by designing a QDBC-based binding assay with a working concentration range of several orders of magnitude and a sub-picomolar detection limit.     

Synthesis and characterization of quantum dot superlattices.

Gold nanoparticles have been synthesized using n-alkylthiol molecules as a passivating agent. By fixing the length of the thiol chain, it is possible to produce nanocrystal arrays, such as 1D chains, 2D arrays of chains and 3D crystals.     

Photochemical properties of a myoglobin-CdTe quantum dot conjugate

A myoglobin-cadmium telluride quantum dot conjugate was constructed using an artificial heme modified with a thiol moiety as a linker. Irradiation of the myoglobin-cadmium telluride conjugate generated the photoreduced ferrous myoglobin via an electron transfer from the photoexcited quantum dot, leading to the formation of CO-bound myoglobin under a CO atmosphere.     

In situ electron-beam polymerization stabilized quantum dot micelles

A polymerizable amphiphile polymer containing PEG was synthesized and used to encapsulate quantum dots in micelles. The quantum dot micelles were then polymerized using a "clean" electron beam process that did not require any post-irradiation purification. Fluorescence spectroscopy revealed that the polymerized micelles provided an organic coating that preserved the quantum dot fluorescence better than nonpolymerized micelles, even under harsh conditions.     

Solution-phase single quantum dot fluorescence resonance energy transfer

We present a single particle fluorescence resonance energy transfer (spFRET) study of freely diffusing self-assembled quantum dot (QD) bioconjugate sensors, composed of CdSe-ZnS core-shell QD donors surrounded by dye-labeled protein acceptors. We first show that there is direct correlation between single particle and ensemble FRET measurements in terms of derived FRET efficiencies and donor-acceptor separation distances. We also find that, in addition to increased sensitivity, spFRET provides information about FRET efficiency distributions which can be used to resolve distinct sensor subpopulations. We use this capacity to gain information about the distribution in the valence of self-assembled QD-protein conjugates and show that this distribution follows Poisson statistics. We then apply spFRET to characterize heterogeneity in single sensor interactions with the substrate/target and show that such heterogeneity varies with the target concentration. The binding constant derived from spFRET is consistent with ensemble measurements.     

Energy levels in self-assembled quantum arbitrarily shaped dots

A model to determine the electronic structure of self-assembled quantum arbitrarily shaped dots is applied. This model is based principally on constant effective mass and constant potentials of the barrier and quantum dot material. An analysis of the different parameters of this model is done and compared with those which take into account the variation of confining potentials, bands, and effective masses due to strain. The results are compared with several spectra reported in literature. By considering the symmetry, the computational cost is reduced with respect to other methods in literature. In addition, this model is not limited by the geometry of the quantum dot.     

Surface-immobilized pyridine-functionalized gamma-cyclodextrin: alkanethiol co-adsorption-induced reorientation

Monolayers of di-6A,6B-deoxy-6-(4-pyridylmethyl)amino-gamma-cyclodextrin (gamma-CD-(py)2) have been formed on polycrystalline platinum electrodes and investigated using electrochemical and surface-enhanced Raman spectroscopy (SERS). The behavior of self-assembled monolayers of (gamma-CD-(py)2) alone, (gamma-CD-(py)2) backfilled with 1-nonanethiol, and 1-nonanethiol are reported. The potential dependence of the capacitance indicates that the film capacitance is higher for the backfilled CD layers than for 1-nonanethiol layers, most likely due to ion flux through the CD cavity. SERS spectra of the backfilled layer exhibit features associated with both pyridine-functionalized CD and alkane moieties. Investigations using [Fe(CN)6]4- as a solution-phase probe indicate that the backfilled CD-alkane thiol layer exhibits enhanced blocking properties compared to gamma-CD-(py)2 films alone. Complete blocking was achieved by a combination of backfilling and insertion of a high-affinity guest 1-adamantylamine into the cavity. Significantly, an electroactive guest with high affinity for gamma-CD, [Co(biptpy)2]2+, does not exhibit a redox response at the gamma-CD-(py)2 layer but molecular recognition is turned on by backfilling the CD layer with 1-nonanethiol molecules. This switching on of the electrochemical activity suggests that the CD hosts are initially inaccessible but reorientate upon backfilling, exposing the CD opening to solution and permitting a supramolecular host-guest complex to form. The binding of [Co(biptpy)2]2+ to gamma-CD in the backfilled monolayer depends on the bulk concentration of guest and is modeled by the Langmuir isotherm, yielding an association constant for the Co2+ state of 1.45 +/- 0.46 x 105 M-1 and a limiting surface coverage 1.49 +/- 0.25 x 10-11 mol cm-2. The surface coverage of the divalent state is higher than the trivalent state, reflecting the dynamic nature of the inclusion.     

ZnS/CdS/ZnS quantum dot quantum well produced in inverted micelles

A ZnS/CdS/ZnS quantum dot quantum well was prepared in AOT micelles successfully and was characterized by absorption spectroscopy and fluorescence spectroscopy. Luminescence in the region of 350-600 nm was observed. The complete ZnS shell might reduce the number of defects on the surface of the CdS well, which were assumed to act as centers for radiationless recombination, resulting in the luminescence enhancement.