Electron Donor-Specific Surface Interactions Promote the Photocatalytic Activity of Metal-Semiconductor Nanohybrids.

In the past two decades, the application of colloidal semiconductor-metal nanoparticles (NPs) as photocatalysts for the hydrogen generation from water has been extensively studied. The present body of literature studies agrees that the photocatalytic yield strongly depends on the electron donating agent (EDA) added for scavenging the photogenerated holes. The highest reported hydrogen production rates are obtained in the presence of ionic EDAs and at high pH. The large hydrogen production rates are attributed to fast hole transfer from the NP onto the EDAs. However, the present discussions do not treat the influence of EDA-specific surface interactions. This systematic study focuses on that aspect by combining steady-state hydrogen production measurements with time-resolved and static optical spectroscopy, employing 11-mercaptoundecanoic acid-capped, Pt-tipped CdSe/CdS dot-in-rods in the presence of a large set of EDAs. Based on the experimental results, two distinct EDA groups are identified: surface-active and diffusion-limited EDAs. The largest photocatalytic efficiencies are obtained in the presence of surface-active EDAs that induce an agglomeration of the NPs. This demonstrates that the introduction of surface-active EDAs can significantly enhance the photocatalytic activity of the NPs, despite reducing their colloidal stability and inducing the formation of NP networks.

Fabrication of Eco-Friendly Wearable Strain Sensor Arrays via Facile Contact Printing for Healthcare Applications.

Wearable flexible strain sensors with spatial resolution enable the acquisition and analysis of complex actions for noninvasive personalized healthcare applications. To provide secure contact with skin and to avoid environmental pollution after usage, sensors with biocompatibility and biodegradability are highly desirable. Herein, wearable flexible strain sensors composed of crosslinked gold nanoparticle (GNP) thin films as the active conductive layer and transparent biodegradable polyurethane (PU) films as the flexible substrate are developed. The patterned GNP films (micrometer- to millimeter-scale square and rectangle geometry, alphabetic characters, and wave and array patterns) are transferred onto the biodegradable PU film via a facile, clean, rapid and high-precision contact printing method, without the need of a sacrificial polymer carrier or organic solvents. The GNP-PU strain sensor with low Young's modulus (≈17.8 MPa) and high stretchability showed good stability and durability (10 000 cycles) as well as degradability (42% weight loss after 17 days at 74 °C in water). The GNP-PU strain sensor arrays with spatiotemporal strain resolution are applied as wearable eco-friendly electronics for monitoring subtle physiological signals (e.g., mapping of arterial lines and sensing pulse waveforms) and large-strain actions (e.g., finger bending).

Solvent controlled 2D structures of bottom-up fabricated nanoparticle superlattices.

We demonstrate that oleyl phosphate ligand-stabilized iron oxide nanocubes as building blocks can be assembled into 2D supercrystalline mono- and multilayers on flat YSZ substrates within a few minutes using a simple spin-coating process. As a bottom-up process, the growth takes place in a layer-by-layer mode and therefore by tuning the spin-coating parameters, the exact number of deposited monolayers can be controlled. Furthermore, ex situ scanning electron and atomic force microscopy as well as X-ray reflectivity measurements give evidence that the choice of solvent allows the control of the lattice type of the final supercrystalline monolayers. This observation can be assigned to the different Hansen solubilities of the solvents used for the nanoparticle dispersion because it determines the size and morphology of the ligand shell surrounding the nanoparticle core. Here, by using toluene and chloroform as solvents, it can be controlled whether the resulting monolayers are ordered in a square or hexagonal supercrystalline lattice.

Kinetic Analysis of the Cation Exchange in Nanorods from Cu2-xS to CuInS2: Influence of Djurleite's Phase Transition Temperature on the Mechanism.

In the syntheses of ternary I-III-VI2 compounds, such as CuInS2, it is often difficult to balance three precursor reactivities to achieve the desired size, shape, and atomic composition of nanocrystals. Cation exchange reactions offer an attractive two-step alternative, by producing a binary compound with the desired morphology and incorporating another atomic species postsynthetically. However, the kinetics of such cation exchange reactions, especially for anisotropic nanocrystals, are still not fully understood. Here, we present the cation exchange reaction from Cu-deficient djurleite Cu2-xS nanorods to wurtzite CuInS2, with size and shape retention. With reaction parameters in a broad temperature range between 40 °C and 160 °C, we were able to obtain various intermediates. Djurleite has a bulk phase transition temperature at 93 °C, which influences the cation exchange considerably. Below the phase transition temperature, indium is only incorporated into the surface of the nanorods, while, at temperatures above the phase transition temperature, we observe a Janus-type exchange mechanism and the formation of CuInS2 bands in the djurleite nanorods. The findings suggest that the diffusion above the phase transition temperature is strongly favored along the copper planes of the copper sulfide nanorods over the diffusion through the sulfur planes. This results in a difference of 37 kJ mol-1 in the activation energy of the cation exchange below and above the phase transition temperature.

Speckle contrast of interfering fluorescence X-rays.

With the development of X-ray free-electron lasers (XFELs), producing pulses of femtosecond durations comparable with the coherence times of X-ray fluorescence, it has become possible to observe intensity-intensity correlations due to the interference of emission from independent atoms. This has been used to compare durations of X-ray pulses and to measure the size of a focusedX-ray beam, for example. Here it is shown that it is also possible to observe the interference of fluorescence photons through the measurement of the speckle contrast of angle-resolved fluorescence patterns. Speckle contrast is often used as a measure of the degree of coherence of the incident beam or the fluctuations of the illuminated sample as determined from X-ray diffraction patterns formed by elastic scattering, rather than from fluorescence patterns as addressed here. Commonly used approaches to estimate speckle contrast were found to suffer when applied to XFEL-generated fluorescence patterns due to low photon counts and a significant variation of the excitation pulse energy from shot to shot. A new method to reliably estimate speckle contrast under such conditions, using a weighting scheme, is introduced. The method is demonstrated by comparing the speckle contrast of fluorescence observed with pulses of 3 fs to 15 fs duration.

Simple one pot synthesis of luminescent europium doped yttrium oxide Y2O3:Eu nanodiscs for phosphor converted warm white LEDs.

Yttrium oxide (Y2O3) is considered as one of the best host lattices for europium (Eu3+) based red emitting phosphors because of its unit cell and good photo-saturation properties. As a bulk material, it reaches nearly 100% quantum yield. However, providing high quality nanosized materials for the LED industry is still a challenge and not easily accomplished. Within this publication, a simple one pot, non-hydrolytic, solvent-based synthesis method for producing uniform and monodisperse red-emitting europium doped yttrium oxide (Y2O3:Eu) nanoparticles is provided. The synthesis is the cheapest and fastest reported yet, yields up to 80%, and offers good scalability, and the diameter of the produced nanodiscs is tunable from 7 nm to 30 nm. The dispersed nanomaterial shows bright red emission (607 nm) under UV excitation (273 nm) and a higher quantum yield (>30%) compared to other nanosized Y2O3:Eu materials. In order to shift the excitation wavelength towards the visible region we added Tb3+ as the sensitizer. Thereby, it was also possible to tune the emission colour towards orange/yellow. Further, a distorted anisotropic cubic Y2O3 phase is confirmed by XRD analysis, resulting in a distinct change in the intensities of red emission transitions. A calcination step transforms it into a highly crystalline cubic phase, known from the bulk material, and exhibiting a typical emission spectrum.

Bulk-like emission in the visible spectrum of colloidal LiYF4:Pr nanocrystals downsized to 10 nm.

Though Pr3+ doped LiYF4 (LiYF4:Pr3+) bulk crystals are a well-known laser gain material with several radiative transitions, their nanocrystal counterparts have not been investigated with regards to these. Through downsizing to the nanoscale, novel applications are expected, especially in composite photonic devices. For example, nanocrystals in stable colloidal form with narrow size distribution are highly desirable to reduce scattering in such composites. Herein, we synthesized monodispersed LiYF4:Pr3+ nanocrystals having a size of 10 nm resulting in colorless clear stable colloidal dispersions and conducted an extensive optical characterization for the first time. We observed unexpected yet intense emission with excited state lifetimes comparable to bulk crystals in the visible spectrum through excitation at 444 nm and 479 nm. In macroscopic bulk crystals, this emission is only exploitable through excitation of a different, subjacent energy level. A comprehensive comparison to the bulk crystals provides deeper insight into the excitation mechanism and performance of these nanocrystals. The presented results pave the way for developing application-oriented LiYF4:Pr3+ nanocrystals as emitters with tailored properties for quantum optics or biomedical applications.

Strengthening Engineered Nanocrystal Three-Dimensional Superlattices via Ligand Conformation and Reactivity.

Nanocrystal assembly into ordered structures provides mesostructural functional materials with a precise control that starts at the atomic scale. However, the lack of understanding on the self-assembly itself plus the poor structural integrity of the resulting supercrystalline materials still limits their application into engineered materials and devices. Surface functionalization of the nanobuilding blocks with organic ligands can be used not only as a means to control the interparticle interactions during self-assembly but also as a reactive platform to further strengthen the final material via ligand cross-linking. Here, we explore the influence of the ligands on superlattice formation and during cross-linking via thermal annealing. We elucidate the effect of the surface functionalization on the nanostructure during self-assembly and show how the ligand-promoted superlattice changes subsequently alter the cross-linking behavior. By gaining further insights on the chemical species derived from the thermally activated cross-linking and its effect in the overall mechanical response, we identify an oxidative radical polymerization as the main mechanism responsible for the ligand cross-linking. In the cascade of reactions occurring during the surface-ligands polymerization, the nanocrystal core material plays a catalytic role, being strongly affected by the anchoring group of the surface ligands. Ultimately, we demonstrate how the found mechanistic insights can be used to adjust the mechanical and nanostructural properties of the obtained nanocomposites. These results enable engineering supercrystalline nanocomposites with improved cohesion while preserving their characteristic nanostructure, which is required to achieve the collective properties for broad functional applications.

Little Adjustments Significantly Simplify the Gram-Scale Synthesis of High-Quality Iron Oxide Nanocubes.

This work presents a facile one-step protocol for the gram-scale synthesis of iron oxide nanocubes with adjustable sizes ranging from 13 to 20 nm and with size distributions between 7 and 12%. As X-ray diffraction indicated the initial formation of the wüstite phase, a formation mechanism of the nanocubes based on the wüstite crystal structure is proposed. When exposed to ambient conditions, the nanoparticles rapidly oxidize to magnetite/maghemite with a remaining wüstite core. The cubic morphology is attributed to the thermodynamic stability of the exposed {100} facets and the control over the growth rate via the use of a sodium oleate/oleic acid mixed ligand system. In contrast to previously reported procedures, the described synthetic approach does not require the initial preparation and isolation of iron oleate. Therefore, the amount of work and the consumption of hazardous solvents are significantly reduced. Thus, the method presented is much more efficient and environmentally more friendly while maintaining excellent control over the particles' shape, size, and size distribution.

Cysteine: an overlooked energy and carbon source.

Biohybrids composed of microorganisms and nanoparticles have emerged as potential systems for bioenergy and high-value compound production from CO2 and light energy, yet the cellular and metabolic processes within the biological component of this system are still elusive. Here we dissect the biohybrid composed of the anaerobic acetogenic bacterium Moorella thermoacetica and cadmium sulphide nanoparticles (CdS) in terms of physiology, metabolism, enzymatics and transcriptomic profiling. Our analyses show that while the organism does not grow on L-cysteine, it is metabolized to acetate in the biohybrid system and this metabolism is independent of CdS or light. CdS cells have higher metabolic activity, despite an inhibitory effect of Cd2+ on key enzymes, because of an intracellular storage compound linked to arginine metabolism. We identify different routes how cysteine and its oxidized form can be innately metabolized by the model acetogen and what intracellular mechanisms are triggered by cysteine, cadmium or blue light.

An in situ and real time study of the formation of CdSe NCs.

Magic Size Clusters (MSCs) have been identified in the last few years as intermediates in the synthesis of nanocrystals (NCs), and ever since there has been increased interest in understanding their exact role in the NC synthesis. Many studies have been focused on understanding the influence of precursors or ligands on the stability of MSCs and on whether the presence of MSCs influences the reaction pathway. However, their kinetic nature calls for an in situ temporal evolution study of the reaction, from the first seconds until the formation of regular nanocrystals, in order to unravel the role of MSCs in the formation of NCs. We have studied the synthesis of CdSe nanocrystals (NCs) in a continuous-flow reactor with in situ optical and small angle X-ray scattering characterization (SAXS). Our results show that MSCs are always formed, regardless the temperature, as necessary intermediates in the formation of CdSe NCs, and that their accumulation in solution depends only on the reaction time. These results explain why MSCs were, in some cases, not observed in some previous studies.

Mapping the Mechanical Properties of Hierarchical Supercrystalline Ceramic-Organic Nanocomposites.

Multiscale ceramic-organic supercrystalline nanocomposites with two levels of hierarchy have been developed via self-assembly with tailored content of the organic phase. These nanocomposites consist of organically functionalized ceramic nanoparticles forming supercrystalline micron-sized grains, which are in turn embedded in an organic-rich matrix. By applying an additional heat treatment step at mild temperatures (250-350 °C), the mechanical properties of the hierarchical nanocomposites are here enhanced. The heat treatment leads to partial removal and crosslinking of the organic phase, minimizing the volume occupied by the nanocomposites' soft phase and triggering the formation of covalent bonds through the organic ligands interfacing the ceramic nanoparticles. Elastic modulus and hardness up to 45 and 2.5 GPa are attained, while the hierarchical microstructure is preserved. The presence of an organic phase between the supercrystalline grains provides a toughening effect, by curbing indentation-induced cracks. A mapping of the nanocomposites' mechanical properties reveals the presence of multiple microstructural features and how they evolve with heat treatment temperature. A comparison with non-hierarchical, homogeneous supercrystalline nanocomposites with lower organic content confirms how the hierarchy-inducing organic excess results in toughening, while maintaining the beneficial effects of crosslinking on the materials' stiffness and hardness.

Seeded Growth Synthesis of Zirconia@Gold Particles in Aqueous Solution.

Metal-ceramic composite particles are of increasing interest due to their potential applications in photonic metamaterials as well as next-generation catalysts. The zirconia-gold system has received little attention due to the lack of controllable preparation methods. Well-known methods for the deposition of gold nanoshells on silica spheres, however, should be adaptable for similar zirconia-based materials. Here, we present a novel synthetic approach to the well-controlled deposition of gold on the surface of sol-gel derived zirconia mesoparticles by a stepwise method involving the immobilization of gold nanoparticles and repeated seeded-growth steps. We show that the immobilization efficiency is strongly enhanced by acidification with hydrochloric acid and additional employment of aminomethylphosphonic acid as coupling agent. The optimum conditions are identified and the subsequent incremental growth by seeded reduction of gold is demonstrated. The results shed light on the parameters governing the preparation of zirconia@gold composite particles and our synthetic approach provides a promising tool for future developments in complex nanomaterials design.

Dielectric response function for colloidal semiconductor quantum dots.

We calculate the optical properties of InP and CdSe colloidal quantum dots (QDs) within the framework of the atomic effective pseudopotential approach and the screened configuration interaction theory. We obtain an excellent agreement with experiment with our microscopic and space-dependent screening function where the dielectric constant varies in real space with a sharp transition (width of ≈0.18 nm) from the QD material high-frequency bulk value inside the QD to the solvent or passivant high-frequency value outside. We obtain a reasonable agreement (with deviations less than 140 meV) for a computationally less demanding solvent-independent screening using the full high-frequency bulk screening, in contrast to the more commonly used reduced QD radius-dependent screening constant. We show theoretically that for QDs passivated with long-chained organic molecules, the influence of the solvent on the optical gap is in the range of 10 meV, while QDs passivated with short ligands can experience shifts in the order of 100 meV. Experiments on CdSe QDs passivated with octadecylphosphonic acid (ODPA, long-chained ligand) in two different solvents (toluene and chloroform) confirm the bandgap dependence. While the optical gap is weakly affected by the environment, the quasiparticle gap and the exciton binding energy show a strong environmental dependence. Finally, we show that the optical bandgap does not depend significantly on the crystal structure (wurtzite or zincblende) or the morphological details (faceted or "spherical" shape).

Modulating the Mechanical Properties of Supercrystalline Nanocomposite Materials via Solvent-Ligand Interactions.

Supercrystalline nanocomposite materials with micromechanical properties approaching those of nacre or similar structural biomaterials can be produced by self-assembly of organically modified nanoparticles and further strengthened by cross-linking. The strengthening of these nanocomposites is controlled via thermal treatment, which promotes the formation of covalent bonds between interdigitated ligands on the nanoparticle surface. In this work, it is shown how the extent of the mechanical properties enhancement can be controlled by the solvent used during the self-assembly step. We find that the resulting mechanical properties correlate with the Hansen solubility parameters of the solvents and ligands used for the supercrystal assembly: the hardness and elastic modulus decrease as the Hansen solubility parameter of the solvent approaches the Hansen solubility parameter of the ligands that stabilize the nanoparticles. Moreover, it is shown that self-assembled supercrystals that are subsequently uniaxially pressed can deform up to 6 %. The extent of this deformation is also closely related to the solvent used during the self-assembly step. These results indicate that the conformation and arrangement of the organic ligands on the nanoparticle surface not only control the self-assembly itself but also influence the mechanical properties of the resulting supercrystalline material. The Hansen solubility parameters may therefore serve as a tool to predict what solvents and ligands should be used to obtain supercrystalline materials with good mechanical properties.

Alumina-Doped Zirconia Submicro-Particles: Synthesis, Thermal Stability, and Microstructural Characterization.

Zirconia nanoceramics are interesting materials for numerous high-temperature applications. Because their beneficial properties are mainly governed by the crystal and microstructure, it is essential to understand and control these features. The use of co-stabilizing agents in the sol-gel synthesis of zirconia submicro-particles should provide an effective tool for adjusting the particles' size and shape. Furthermore, alumina-doping is expected to enhance the particles' size and shape persistence at high temperatures, similar to what is observed in corresponding bulk ceramics. Dispersed alumina should inhibit grain growth by forming diffusion barriers, additionally impeding the martensitic phase transformation in zirconia grains. Here, alumina-doped zirconia particles with sphere-like shape and average diameters of ∼ 300 n m were synthesized using a modified sol-gel route employing icosanoic acid and hydroxypropyl cellulose as stabilizing agents. The particles were annealed at temperatures between 800 and 1200 ∘ C and characterized by electron microscopy, elemental analysis, and X-ray diffraction. Complementary elemental analyses confirmed the precise control over the alumina content (0-50 mol%) in the final product. Annealed alumina-doped particles showed more pronounced shape persistence after annealing at 1000 ∘ C than undoped particles. Quantitative phase analyses revealed an increased stabilization of the tetragonal/cubic zirconia phase and a reduced grain growth with increasing alumina content. Elemental mapping indicated pronounced alumina segregation near the grain boundaries during annealing.

Elasticity of Cross-Linked Titania Nanocrystal Assemblies Probed by AFM-Bulge Tests.

In order to enable advanced technological applications of nanocrystal composites, e.g., as functional coatings and layers in flexible optics and electronics, it is necessary to understand and control their mechanical properties. The objective of this study was to show how the elasticity of such composites depends on the nanocrystals' dimensionality. To this end, thin films of titania nanodots (TNDs; diameter: ~3-7 nm), nanorods (TNRs; diameter: ~3.4 nm; length: ~29 nm), and nanoplates (TNPs; thickness: ~6 nm; edge length: ~34 nm) were assembled via layer-by-layer spin-coating. 1,12-dodecanedioic acid (12DAC) was added to cross-link the nanocrystals and to enable regular film deposition. The optical attenuation coefficients of the films were determined by ultraviolet/visible (UV/vis) absorbance measurements, revealing much lower values than those known for titania films prepared via chemical vapor deposition (CVD). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed a homogeneous coverage of the substrates on the µm-scale but a highly disordered arrangement of nanocrystals on the nm-scale. X-ray photoelectron spectroscopy (XPS) analyses confirmed the presence of the 12DAC cross-linker after film fabrication. After transferring the films onto silicon substrates featuring circular apertures (diameter: 32-111 µm), freestanding membranes (thickness: 20-42 nm) were obtained and subjected to atomic force microscopy bulge tests (AFM-bulge tests). These measurements revealed increasing elastic moduli with increasing dimensionality of the nanocrystals, i.e., 2.57 ± 0.18 GPa for the TND films, 5.22 ± 0.39 GPa for the TNR films, and 7.21 ± 1.04 GPa for the TNP films.

Ligand density on nanoparticles: A parameter with critical impact on nanomedicine.

Nanoparticles modified with ligands for specific targeting towards receptors expressed on the surface of target cells are discussed in literature towards improved delivery strategies. In such concepts the ligand density on the surface of the nanoparticles plays an important role. How many ligands per nanoparticle are best for the most efficient delivery? Importantly, this number may be different for in vitro and in vivo scenarios. In this review first viruses as "biological" nanoparticles are analyzed towards their ligand density, which is then compared to the ligand density of engineered nanoparticles. Then, experiments are reviewed in which in vitro and in vivo nanoparticle delivery has been analyzed in terms of ligand density. These results help to understand which ligand densities should be attempted for better targeting. Finally synthetic methods for controlling the ligand density of nanoparticles are described.

Cross-Linked Polystyrene Shells Grown on Iron Oxide Nanoparticles via Surface-Grafted AGET-ATRP in Microemulsion.

Most applications of nanoparticles require robust stabilization, for example, by surface-bound ligands or the encapsulation within polymer shells. Furthermore, for biomedical applications, the particles must be dispersible in a complex biological environment. Thus, high-quality nanoparticles synthesized in organic solvents must be transferred into aqueous media. Here, we present a novel scalable method enabling the robust hydrophilic encapsulation of non-agglomerated nanoparticles by growing polystyrene shells via AGET-ATRP in microemulsion. To demonstrate this approach, we encapsulate iron oxide nanoparticles (diameter: 13.7 ± 0.6 nm). Because the ATRP initiator is grafted onto the nanoparticles' surface, the shells are covalently attached to the iron oxide cores. By varying the amount of monomers, the shell thickness can be adjusted precisely, as indicated by the increasing hydrodynamic size from ∼22 to 26 nm (DLS, number mean) with an increasing amount of added monomers. Moreover, the degree of cross-linking can be controlled by the amount of added divinylbenzene (DVB). To evaluate the robustness of the polymer shells against ion infusion, we introduce a novel colorimetric method, which is based on the formation of the red iron thiocyanate complex. After addition of HCl, the increase in absorbance at 468 nm indicates leaching of iron ions from the polymer-encapsulated core particles. These measurements confirm that with increasing shell thickness, significantly improved shielding is achieved. Furthermore, high concentrations of added DVB [33-50% (v/v) in a monomer mixture] improve the shielding effect. However, when smaller amounts of DVB were added [10-25% (v/v)], the shielding effect was diminished, even in comparison to non-cross-linked polymer shells. This finding suggests a higher porosity of shells with a low degree of cross-linking.

Hierarchical supercrystalline nanocomposites through the self-assembly of organically-modified ceramic nanoparticles.

Biomaterials often display outstanding combinations of mechanical properties thanks to their hierarchical structuring, which occurs through a dynamically and biologically controlled growth and self-assembly of their main constituents, typically mineral and protein. However, it is still challenging to obtain this ordered multiscale structural organization in synthetic 3D-nanocomposite materials. Herein, we report a new bottom-up approach for the synthesis of macroscale hierarchical nanocomposite materials in a single step. By controlling the content of organic phase during the self-assembly of monodisperse organically-modified nanoparticles (iron oxide with oleyl phosphate), either purely supercrystalline or hierarchically structured supercrystalline nanocomposite materials are obtained. Beyond a critical concentration of organic phase, a hierarchical material is consistently formed. In such a hierarchical material, individual organically-modified ceramic nanoparticles (Level 0) self-assemble into supercrystals in face-centered cubic superlattices (Level 1), which in turn form granules of up to hundreds of micrometers (Level 2). These micrometric granules are the constituents of the final mm-sized material. This approach demonstrates that the local concentration of organic phase and nano-building blocks during self-assembly controls the final material's microstructure, and thus enables the fine-tuning of inorganic-organic nanocomposites' mechanical behavior, paving the way towards the design of novel high-performance structural materials.