Segmental Mobility Studies of Poly(N-isopropyl acrylamide) Interactions with Gold Nanoparticles and Its Use as a Thermally Driven Trapping System.

Thermal desolvation of poly(N-isopropylacrylamide) (PNIPAM) in the presence of a low concentration of gold nanoparticles incorporates the nanoparticles resulting in suspended aggregates. By covalently incorporating <1% acenaphthylene into the polymerization feed this copolymer is enabled to be used as a model to study the segmental mobility of the PNIPAM backbone in response to gold nanoparticles both below and above the desolvation temperature, showing that there is a physical conformational rearrangement of the soluble polymer at ultralow nanoparticle loadings, indicating low affinity interactions with the nanoparticles. Thermal desolvation is capable of extracting >99.9% of the nanoparticles from their solutions and hence demonstrates that poly(N-isopropylacrylamide) can act as an excellent scrubbing system to remove metallic nanomaterial pollutants from solution.

Absolute Energy Level Positions in CdSe Nanostructures from Potential-Modulated Absorption Spectroscopy (EMAS).

Semiconductor nanostructures such as CdSe quantum dots and colloidal nanoplatelets exhibit remarkable optical properties, making them interesting for applications in optoelectronics and photocatalysis. For both areas of application a detailed understanding of the electronic structure is essential to achieve highly efficient devices. The electronic structure can be probed using the fact that optical properties of semiconductor nanoparticles are found to be extremely sensitive to the presence of excess charges that can for instance be generated by means of an electrochemical charge transfer via an electrode. Here we present the use of EMAS as a versatile spectroelectrochemical method to obtain absolute band edge positions of CdSe nanostructures versus a well-defined reference electrode under ambient conditions. In this, the spectral properties of the nanoparticles are monitored with respect to an applied electrochemical potential. We developed a bleaching model that yields the lowest electronic state in the conduction band of the nanostructures. A change in the band edge positions caused by quantum confinement is shown both for CdSe quantum dots and for colloidal nanoplatelets. In the case of CdSe quantum dots these findings are in good agreement with tight binding calculations. The method presented is not limited to CdSe nanostructures but can be used as a universal tool. Hence, this technique allows the determination of absolute band edge positions of a large variety of materials used in various applications.

The distribution and degradation of radiolabeled superparamagnetic iron oxide nanoparticles and quantum dots in mice.

(51)Cr-labeled, superparamagnetic, iron oxide nanoparticles ((51)Cr-SPIOs) and (65)Zn-labeled CdSe/CdS/ZnS-quantum dots ((65)Zn-Qdots) were prepared using an easy, on demand, exchange-labeling technique and their particokinetic parameters were studied in mice after intravenous injection. The results indicate that the application of these heterologous isotopes can be used to successfully mark the nanoparticles during initial distribution and organ uptake, although the (65)Zn-label appeared not to be fully stable. As the degradation of the nanoparticles takes place, the individual transport mechanisms for the different isotopes must be carefully taken into account. Although this variation in transport paths can bring new insights with regard to the respective trace element homeostasis, it can also limit the relevance of such trace material-based approaches in nanobioscience. By monitoring (51)Cr-SPIOs after oral gavage, the gastrointestinal non-absorption of intact SPIOs in a hydrophilic or lipophilic surrounding was measured in mice with such high sensitivity for the first time. After intravenous injection, polymer-coated, (65)Zn-Qdots were mainly taken up by the liver and spleen, which was different from that of ionic (65)ZnCl2. Following the label for 4 weeks, an indication of substantial degradation of the nanoparticles and the release of the label into the Zn pool was observed. Confocal microscopy of rat liver cryosections (prepared 2 h after intravenous injection of polymer-coated Qdots) revealed a colocalization with markers for Kupffer cells and liver sinusoidal endothelial cells (LSEC), but not with hepatocytes. In J774 macrophages, fluorescent Qdots were found colocalized with lysosomal markers. After 24 h, no signs of degradation could be detected. However, after 12 weeks, no fluorescent nanoparticles could be detected in the liver cryosections, which would confirm our (65)Zn data showing a substantial degradation of the polymer-coated CdSe/CdS/ZnS-Qdots in the liver.

Ultrasmall SnO2 nanocrystals: hot-bubbling synthesis, encapsulation in carbon layers and applications in high capacity Li-ion storage.

Ultrasmall SnO2 nanocrystals as anode materials for lithium-ion batteries (LIBs) have been synthesized by bubbling an oxidizing gas into hot surfactant solutions containing Sn-oleate complexes. Annealing of the particles in N2 carbonifies the densely packed surface capping ligands resulting in carbon encapsulated SnO2 nanoparticles (SnO2/C). Carbon encapsulation can effectively buffer the volume changes during the lithiation/delithiation process. The assembled SnO2/C thus deliver extraordinarily high reversible capacity of 908 mA·h·g(-1) at 0.5 C as well as excellent cycling performance in the LIBs. This method demonstrates the great potential of SnO2/C nanoparticles for the design of high power LIBs.

Interconnection of nanoparticles within 2D superlattices of PbS/oleic acid thin films.

Make it connected! 2D close-packed layers of inorganic nanoparticles are interconnected by organic fibrils of oleic acid as clearly visualized by electron holography. These fibrils can be mineralised by PbS to transform an organic-inorganic framework to a completely interconnected inorganic semiconducting 2D array.

Synthesis of radioactively labelled CdSe/CdS/ZnS quantum dots for in vivo experiments.

During the last decades of nanoparticles research, many nanomaterials have been developed for applications in the field of bio-labelling. For the visualization of transport processes in the body, organs and cells, luminescent quantum dots (QDs) make for highly useful diagnostic tools. However, intercellular routes, bio-distribution, metabolism during degradation or quantification of the excretion of nanoparticles, and the study of the biological response to the QDs themselves are areas which to date have not been fully investigated. In order to aid in addressing those issues, CdSe/CdS/ZnS QDs were radioactively labelled, which allows quantification of the QD concentration in the whole body or in ex vivo samples by γ-counting. However, the synthesis of radioactively labelled QDs is not trivial since the coating process must be completely adapted, and material availability, security and avoidance of radioactive waste must be considered. In this contribution, the coating of CdSe/CdS QDs with a radioactive (65)ZnS shell using a modified, operator-safe, SILAR procedure is presented. Under UV illumination, no difference in the photoluminescence of the radioactive and non-radioactive CdSe/CdS/ZnS colloidal solutions was observed. Furthermore, a down-scaled synthesis for the production of very small batches of 5 nmol QDs without loss in the fluorescence quality was developed. Subsequently, the radio-labelled QDs were phase transferred by encapsulation into an amphiphilic polymer. γ-counting of the radioactivity provided confirmation of the successful labelling and phase transfer of the QDs.

Emissive ZnO@Zn3 P2 nanocrystals: synthesis, optical, and optoelectrochemical properties.

ZnO@Zn3 P2 quantum dots (QDs) are synthesized, with emission from yellow to red. Photoelectrochemical investigations reveal that the current and voltage of the QD-derivatized electrodes show a response upon illumination. A photocurrent of ca. 8 nA cm(-2) for a monolayer of ZnO@Zn3 P2 QDs deposited on indium tin oxide (ITO) electrode is recorded.

Quantum-dot-based photoelectrochemical sensors for chemical and biological detection.

Quantum-dot-based photoelectrochemical sensors are powerful alternatives for the detection of chemicals and biochemical molecules compared to other sensor types, which is the primary reason as to why they have become a hot topic in nanotechnology-related analytical methods. These sensors basically consist of QDs immobilized by a linking molecule (linker) to an electrode, so that upon their illumination, a photocurrent is generated which depends on the type and concentration of the respective analyte in the immediate environment of the electrode. The present review provides an overview of recent developments in the fabrication methods and sensing concepts concerning direct and indirect interactions of the analyte with quantum dot modified electrodes. Furthermore, it describes in detail the broad range of different sensing applications of such quantum-dot-based photoelectrochemical sensors for inorganic and organic (small and macro-) molecules that have arisen in recent years. Finally, a number of aspects concerning current challenges on the way to achieving real-life applications of QD-based photochemical sensing are addressed.

Stimuli-responsive hierarchically self-assembled 3D porous polymer-based structures with aligned pores.

We have developed a novel approach for the fabrication of self-assembled porous materials with uniaxial tubular pores. The approach is based on the use of microtubes formed by stimuli-induced rolling of polymer bilayers consisting of hydrophobic and stimuli-responsive hydrophilic polymers. Different objects, for example yeast cells, can be encapsulated inside the tubes during their rolling. The self-rolled tubes filled with the yeast cells are capable of controlled self-assembly and form a uniaxial tubular homogeneously filled scaffold. Moreover, our approach allows design of porous materials with the pores having different properties.

Large-area (over 50 cm × 50 cm) freestanding films of colloidal InP/ZnS quantum dots.

We propose and demonstrate the fabrication of flexible, freestanding films of InP/ZnS quantum dots (QDs) using fatty acid ligands across very large areas (greater than 50 cm × 50 cm), which have been developed for remote phosphor applications in solid-state lighting. Embedded in a poly(methyl methacrylate) matrix, although the formation of stand-alone films using other QDs commonly capped with trioctylphosphine oxide (TOPO) and oleic acid is not efficient, employing myristic acid as ligand in the synthesis of these QDs, which imparts a strongly hydrophobic character to the thin film, enables film formation and ease of removal even on surprisingly large areas, thereby avoiding the need for ligand exchange. When pumped by a blue LED, these Cd-free QD films allow for high color rendering, warm white light generation with a color rendering index of 89.30 and a correlated color temperature of 2298 K. In the composite film, the temperature-dependent emission kinetics and energy transfer dynamics among different-sized InP/ZnS QDs are investigated and a model is proposed. High levels of energy transfer efficiency (up to 80%) and strong donor lifetime modification (from 18 to 4 ns) are achieved. The suppression of the nonradiative channels is observed when the hybrid film is cooled to cryogenic temperatures. The lifetime changes of the donor and acceptor InP/ZnS QDs in the film as a result of the energy transfer are explained well by our theoretical model based on the exciton-exciton interactions among the dots and are in excellent agreement with the experimental results. The understanding of these excitonic interactions is essential to facilitate improvements in the fabrication of photometrically high quality nanophosphors. The ability to make such large-area, flexible, freestanding Cd-free QD films pave the way for environmentally friendly phosphor applications including flexible, surface-emitting light engines.

Synthesis of monodisperse cadmium phosphide nanoparticles using ex-situ produced phosphine.

The synthesis of nanoparticles using a gas-liquid interfacial reaction, which for the first time is shown to result in highly monodisperse materials across a range of sizes, is presented. We demonstrate, using cadmium phosphide as the paradigm that this synthesis method can provide colloidal nanocrystals or quantum dots monodisperse enough so that for the first time multiple transitions in their absorbance spectra can be observed. Clear evidence is given that the resulting cadmium material is Cd(6)P(7) and not Cd(3)P(2), and a thorough investigation into the role of temperature and growth time and their effects on the optical properties has been conducted. This strategy can be extended to synthesize other relevant members of the binary component pnictide semiconducting family, and the chemistry of the pnictide compound formation using this synthetic methodology has been explained using the redox potential of the metals. The suitability of the resulting cadmium phosphide quantum dots for applications in light-emitting diodes (LEDs) has further been demonstrated.

High efficiency quantum dot heterojunction solar cell using anatase (001) TiO2 nanosheets.

This is the first report of using anatase TiO(2) nanosheets with exposed (001) facets in a high-efficiency PbS quantum dot/TiO(2) heterojunction solar cell. The TiO(2) nanosheets have higher conduction band, and surface energy compared to normal anatase (101) TiO(2) nanoparticles. This PbS QD/TiO(2) heterojunction solar cell produces power conversion efficiency of 4.7% which is one of the highest reported in literature.

Light energy conversion by mesoscopic PbS quantum dots/TiO2 heterojunction solar cells.

Solid state PbS quantum dots (QDs)/TiO(2) heterojunction solar cells were produced by depositing PbS QDs on a 500 nm thick mesoscopic TiO(2) films using layer-by-layer deposition. Importantly, the PbS QDs act here as photosensitizers and at the same time as hole conductors. The PbS QDs/TiO(2) device produces a short circuit photocurrent (J(sc)) of 13.04 mA/cm(2), an open circuit photovoltage (V(oc)) of 0.55 V and a fill factor (FF) of 0.49, corresponding to a light to electric power conversion efficiency (η) of 3.5% under AM1.5 illumination. The electronic processes occurring in this device were investigated by transient photocurrent and photovoltage measurements as well as impedance spectroscopy in the dark and under illumination. The investigations showed a high resistivity for the QD/metal back contact, which reduces drastically under illumination. EIS also indicated a shift of the depletion layer capacitance under illumination related to the change of the dipole at this interface.

Progress in the light emission of colloidal semiconductor nanocrystals.

Some 25 years ago it was found that semiconductor nanocrystals emitted light. Since then tremendous progress has been made with respect to increasing the emission quantum yields, extending the spectral range that may be addressed, from the UV across to the near infrared, and improving the color purity. Here some major lines in these developments are reviewed, touching on milestones as well as on the principles of the most successful preparative approaches.

Synthesis and characterization of cadmium phosphide quantum dots emitting in the visible red to near-infrared.

The synthesis of high-quality cadmium phosphide quantum dots with emission wavelength maxima in the range from 1200 to approximately 760 nm are reported. The results demonstrate that the nucleation and growth linked with the optical properties can be controlled by the temperature, the growth time, and the addition of ligands such as oleylamine and trioctylphosphine. Photoelectrochemical investigations revealed that the cadmium phosphide QD-derivatized electrodes show an optical response and that photocurrents of several nanoamperes per square centimeter can be obtained upon illumination.

Size and shape control of colloidally synthesized IV-VI nanoparticulate tin(II) sulfide.

We report the synthesis and characterization of monodisperse SnS nanocrystals and demonstrate shape control by varying the ratio of ligands present in the reaction mixture. The nanoparticles are subsequently linked to conducting transparent substrates, and their optoelectronic response is probed. Values of the photocurrent for this system, without attempts to optimize, in the range of 6-8 nA cm(-2) were obtained.

Infrared-emitting colloidal nanocrystals: synthesis, assembly, spectroscopy, and applications.

Semiconductor nanocrystals produced by means of colloidal chemistry in a solvent medium are an attractive class of nanometer-sized building blocks from which to create complex materials with unique properties for a variety of applications. Their optical and electronic properties can be tailored easily, both by their chemical composition and particle size. While colloidal nanocrystals emitting in the infrared region have seen a burst of attention during the last decade there is clearly a paucity of review articles covering their synthesis, assembly, spectroscopic characterization, and applications. This Review comprehensively addresses these topics for II-VI, III-V, and IV-VI nanocrystals, examples being HgTe and Cd(x)Hg(1-) (x)Te, InP and InAs, and PbS, PbSe, and PbTe, respectively. Among the applications discussed here are optical amplifier media for telecommunications systems, electroluminescence devices, and noninvasive optical imaging in biology.