Lipid-based systems loaded with PbS nanocrystals: near infrared emitting trackable nanovectors

Hydrophobic PbS nanocrystals (NCs) emitting in the near infrared spectral region were encapsulated in the core of micelles and in the bilayer of liposomes, respectively, to form polyethylene glycol (PEG)-grafted phospholipids. The phospholipid-based functionalization process of PbS NCs required the replacement of the pristine capping ligand at the NC surface with thiol molecules. The procedures carried out for two systems, micelles and liposomes, using PEG-modified phospholipids were carefully monitored by optical, morphological and structural investigations. The hydrodynamic diameter and the colloidal stability of both micelles and liposomes loaded with PbS NCs were evaluated using Dynamic Light Scattering (DLS) and z-potential experiments, and both were satisfactorily stable in physiological media. The cytotoxicity of the resulting PbS NC-loaded nanovectors was assessed by the in vitro investigation on Saos-2 cells, indicating that the toxicity of the PbS NC loaded liposomes was lower than that of the micelles with the same NC cargo, which is reasonable due to the different overall composition of the two prepared nanocarriers. Finally, the cellular uptake in the Saos-2 cells of both the NC containing systems was evaluated by means of confocal microscopy studies by exploiting a visible fluorescent phospholipid and demonstrating the ability of both luminescent nanovectors to be internalized. The obtained results show the great potential of the prepared emitting nanoprobes for imaging applications in the second biological window

Radiative exciton recombination dynamics in QD-tagged polystyrene microspheres

Fluorescent polystyrene microspheres are prepared by the incorporation of fluorescent CdSe/CdS core/shell semiconductor nanocrystals (quantum dots, QDs) using the emulsification/solvent evaporation method. The radiative exciton recombination dynamics is investigated by nanosecond time-resolved fluorescence spectroscopy at ambient conditions. The time constants of fast and slow fluorescence decay in QDs, dispersed in toluene, were 3.5 and 17.8 ns, respectively. For the QD-tagged microspheres, the time constants of fast and slow processes were similar to 2-3 and similar to 11-12 ns, respectively, and did not depend significantly on the QD-content of the microspheres. The fast decay component could be attributed to the recombination of delocalized exciton in the internal core states, and the slow component was attributed to the localized exciton in the surface states. It was found that the ratio of amplitudes of the fast and slow processes also changed after incorporation of QDs in microspheres. The observed differences in fluorescence decay between non-entrapped QDs and QD-tagged microspheres were probably due to energy transfer between the nanocrystals, which were in close proximity inside the microspheres. The obtained fluorescent QD-tagged microspheres are characterized by the other methods as well, which makes them of value for various applications as optical materials

Patterned assembly of luminescent nanocrystals: Role of the molecular chemistry at the interface

A simple fabrication approach for achieving nanoparticle patterns based on a room temperature chemically driven strategy is reported. Suitably engineered colloidal luminescent nanocrystals (NCs) (4 and 6 nm in diameter), namely organic capped and silica-coated negatively charged CdSe@ZnS NCs, have been selectively assembled onto defined domains in a binary hydrophobic/hydrophilic chemical pattern, purposely fabricated by combining microcontact printing and wet chemistry procedures. The goal of the work has been to investigate the experimental parameters governing the assembly process at molecular level, in order to elucidate factors regulating interactions at the interfaces. For this purpose, specific sets of conditions, namely substrate patterns and NCs with distinct surface functionalization, have been prepared and tested using different NC dispersing solvents. The NC assembly has been demonstrated driven by non-covalent forces, namely Van der Waals or electrostatic interactions occurring at the NC/substrate interface. The overall study has provided a comprehensive understanding of the role of solvent and molecular chemistry at interfaces in NC assembling. The obtained results can be valuable to set up reliable procedures for developing reproducible patterning protocols potentially useful for the fabrication of NC-based devices. © 2014 Springer Science+Business Media

A Meso-Crystallographic study of a 3D Self-assembled bi-modal Nanocrystal Superlattice

Nanocrystal superlattices are attracting significant interest due to novel and peculiar collective properties arising from the interactions of the nanocrystals forming the superlattice. A large variety of superlattice structures can be obtained, involving one or more types of nanocrystals, with different size and concentrations. Engineering of the superlattice properties relies on accurate structural and morphological characterization, able to provide not only a fundamental feedback for synthesis procedures, but also relevant insight on their structural properties for possible applications. Electron microscopy and X-ray based techniques are complementary approaches for nanoscale structural imaging, which however becomes challenging in presence of building blocks only a few nm in size. Here, a structure solution for a 3D self-assembly of PbS nanocrystals with bi-modal size distribution is obtained, by exploiting small angle X-ray diffraction, transmission electron microscopy, crystallographic procedures, and geometric constraints. In particular, analysis of small angle X-ray diffraction data, based on the Patterson function and on single crystal model, is shown to provide relevant information on the 3D superlattice structure as well as on particle size, the scattering signal being sensitive to particles as small as 1.5 nm. The combined approach here proposed is thus demonstrated to effectively overcome important resolution limitations in the imaging of superlattices including small nanocrystals

Near Infrared Emission from Monomodal and Bimodal PbS Nanocrystal Superlattices

PbS colloidal nanocrystal (NC) assemblies with monomodal and bimodal size distribution have been fabricated by slow evaporation of solvent on silicon substrates. The interparticle distances of the assembled structures have been carefully defined, both in the plane and in the z-direction, perpendicular to the substrate, thanks to the combination of small and wide angle X-ray diffraction and TEM measurements. The spectroscopic characteristics of PbS NCs, both in solution and organized in a superlattice, have been investigated by steady-state and time-resolved photoluminescence measurements. The optical results reveal the occurrence of a Förster Resonant Energy Transfer (FRET) mechanism between closed-packed neighboring PbS NCs. The occurrence of FRET is dependent on NC assembly geometry, and thus on their interparticle distance, suggesting that only when NCs are close enough, as in the close-packed arrangement of the monomodal assembly, the energy transfer can be promoted. In bimodal assemblies, the energy transfer between large and small NCs is negligible, due to the low spectral overlap between the emission and absorption bands of the different sized nanoparticles, and to the large interparticle distance. Moreover, recombination lifetimes on the microsecond time scale have been observed and explained in terms of dielectric screening effect, in agreement with previous findings on lead chalcogenide NC optical properties

Near Infrared Emission from Monomodal and Bimodal PbS Nanocrystal Superlattices

PbS colloidal nanocrystal (NC) assemblies with monomodal and bimodal size distribution have been fabricated by slow evaporation of solvent on silicon substrates. The interparticle distances of the assembled structures have been carefully defined, both in the plane and in the z-direction, perpendicular to the substrate, thanks to the combination of small and wide angle X-ray diffraction and TEM measurements. The spectroscopic characteristics of PbS NCs, both in solution and organized in a superlattice, have been investigated by steady-state and time-resolved photoluminescence measurements. The optical results reveal the occurrence of a Förster Resonant Energy Transfer (FRET) mechanism between closed-packed neighboring PbS NCs. The occurrence of FRET is dependent on NC assembly geometry, and thus on their interparticle distance, suggesting that only when NCs are close enough, as in the close-packed arrangement of the monomodal assembly, the energy transfer can be promoted. In bimodal assemblies, the energy transfer between large and small NCs is negligible, due to the low spectral overlap between the emission and absorption bands of the different sized nanoparticles, and to the large interparticle distance. Moreover, recombination lifetimes on the microsecond time scale have been observed and explained in terms of dielectric screening effect, in agreement with previous findings on lead chalcogenide NC optical properties

Near Infrared Emission from Monomodal and Bimodal PbS Nanocrystal Superlattices

PbS colloidal nanocrystal (NC) assemblies with monomodal and bimodal size distribution have been fabricated by slow evaporation of solvent on silicon substrates. The interparticle distances of the assembled structures have been carefully defined, both in the plane and in the z direction, perpendicular to the substrate, thanks to the combination of small and wide-angle X-ray diffraction and TEM measurements. The spectroscopic characteristics of PbS NCs, both in solution and organized in a superlattice, have been investigated by steady-state and time-resolved photoluminescence measurements. The optical results reveal the occurrence of a Forster resonant energy transfer (FRET) mechanism between closed-packed neighboring PbS NCs. The occurrence of FRET is dependent on NC assembly geometry, and thus on their interparticle distance, suggesting that only when NCs are close enough, as in the close-packed arrangement of the monomodal assembly, the energy transfer can be promoted. In bimodal assemblies, the energy transfer between large and small NCs is negligible, due to the low spectral overlap between the emission and absorption bands of the different sized nanoparticles and to the large interparticle distance. Moreover, recombination lifetimes on the microsecond time scale have been observed and explained in terms of dielectric screening effect, in agreement with previous findings on lead chalcogenide NC optical properties

H-bonding driven assembly of colloidal Au nanoparticles on nanostructured poly(styrene-b-ethylene oxide) block copolymer templates

A facile, cost-effective, and general solution-based "bottom-up" method for nanopatterning dense arrays of colloidal Au nanoparticles (NPs) has been developed. The organization of the NPs has been successfully achieved onto a microphase-separated poly(styrene-block-ethylene oxide) (PS-b-PEO) block copolymer (BCP) thin film which acts as structural template. The NP assembly process occurs by incubating the BCP films in dispersions of the ex situ synthesized Au NPs, not requiring any chemical pre-treatment or activation step of the copolymer surface, and has demonstrated to be distinctively controlled by multiple, cooperative, and selective hydrogen bonding interactions between hydroxyl functionalities of the capping molecules coating the Au NP surface and the hydrophilic PEO block. The effect of incubation time and concentration of NPs on the selectivity of the assembly has been investigated by atomic force and scanning electron microscopy. The results show that the BCP pattern is preserved after decoration with the Au NPs. The fabricated nanopatterns are good candidates for nanostructure integration in sensing and optoelectronic applications, as well as in memory devices and photonic systems. Moreover, the proposed immobilization protocol represents a model system that can be extended to other NPs having different compositions and surface chemistries

Au nanoparticle: In situ decorated RGO nanocomposites for highly sensitive electrochemical genosensors

A novel hybrid nanocomposite formed by RGO flakes, surface functionalized by 1-pyrene carboxylic acid (PCA), densely and uniformly in situ decorated by Au NPs, that are concomitantly coordinated by the PCA carboxylic group, and by an aromatic thiol used as the reducing agent in the synthesis, both ensuring, at the same time, a stable non-covalent NPs anchorage to the RGO flakes, and an efficient interparticle electron coupling along the NP network onto the RGO, is reported. The obtained solution processable hybrid material is used to modify Screen-Printed Carbon Electrodes (SPCEs). The hybrid modified SPCEs, functionalized with a thiolated DNA capture probe, are tested in a streptavidin-alkaline-phosphatase catalyzed assay, for the detection of the biotinylated miRNA-221, and for its determination in spiked human blood serum samples. The proposed genosensor demonstrates a high sensitivity (LOD of 0.7 pM), attesting for a performance comparable with the most effective reported sensors. The enhanced sensitivity is explained in terms of the very fast heterogeneous electron transfer kinetics, the concomitant decrease of the electron transfer resistance at the electrode/electrolyte interface, the high electroactivity and the high surface area of the nanostructured hybrid modified SPCEs that provide a convenient platform for nucleic acid biosensing

Self-organization of mono- and bi-modal PbS nanocrystal populations in superlattices

Here the synthesis of distinct monomodal and bimodal PbS nanocrystal (NC) populations, with narrow size-distribution, is reported. The ability to achieve careful control of NC size and size distribution allowed the preparation, in one single synthetic step, of two distinct populations of PbS NCs, with tuneable size ratio. The NC growth was carefully studied in order to gain insight into the mechanism underlying the formation of the mono and bimodal PbS NC families. The synthesized PbS NCs were structurally and chemically characterized, and subsequently used as building blocks for fabricating solid crystal assemblies by solvent evaporation. In particular the role played by different parameters, namely NC size and concentration, dispersing solvent and substrate, on crystallinity, geometry and structure of the obtained solids was systematically investigated. Interestingly the assembly of bimodal PbS NC samples leads to the formation of diverse superlattice structures, with a final geometry dependent on the NC size and the size ratio in the bimodal population. The synthetic procedure was then ultimately responsible of the superlattice structures, through the control of the PbS NC size and size ratio in the bimodal population