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.

Organically linked iron oxide nanoparticle supercrystals with exceptional isotropic mechanical properties.

It is commonly accepted that the combination of the anisotropic shape and nanoscale dimensions of the mineral constituents of natural biological composites underlies their superior mechanical properties when compared to those of their rather weak mineral and organic constituents. Here, we show that the self-assembly of nearly spherical iron oxide nanoparticles in supercrystals linked together by a thermally induced crosslinking reaction of oleic acid molecules leads to a nanocomposite with exceptional bending modulus of 114 GPa, hardness of up to 4 GPa and strength of up to 630 MPa. By using a nanomechanical model, we determined that these exceptional mechanical properties are dominated by the covalent backbone of the linked organic molecules. Because oleic acid has been broadly used as nanoparticle ligand, our crosslinking approach should be applicable to a large variety of nanoparticle systems.

A universal approach to ultrasmall magneto-fluorescent nanohybrids.

Seeded emulsion polymerization is a powerful universal method to produce ultrasmall multifunctional magnetic nanohybrids. In a two-step procedure, iron oxide nanocrystals were initially encapsulated in a polystyrene (PS) shell and subsequently used as beads for a controlled assembly of elongated quantum dots/quantum rods (QDQRs). The synthesis of a continuous PS shell allows the whole construct to be fixed and the composition of the nanohybrid to be tuned. The fluorescence of the QDQRs and magnetism of iron oxide were perfectly preserved, as confirmed by single-particle investigation, fluorescence decay measurements, and relaxometry. Bio-functionalization of the hybrids was straightforward, involving copolymerization of appropriate affinity ligands as shown by immunoblot analysis. Additionally, the universality of this method was shown by the embedment of a broad scale of NPs.

Polymer-assisted self-assembly of superparamagnetic iron oxide nanoparticles into well-defined clusters: controlling the collective magnetic properties.

The combination of superstructure-forming amphiphilic block copolymers and superparamagnetic iron oxide nanoparticles produces new nano/microcomposites with unique size-dependent properties. Herein, we demonstrate the controlled clustering of superparamagnetic iron oxide nanoparticles (SPIOs) ranging from discretely encapsulated SPIOs to giant clusters, containing hundreds or even more particles, using an amphiphilic polyisoprene-block-poly(ethylene glycol) diblock copolymer. Within these clusters, the SPIOs interact with each other and show new collective properties, neither obtainable with singly encapsulated nor with the bulk material. We observed cluster-size-dependent magnetic properties, influencing the blocking temperature, the magnetoviscosity of the liquid suspension, and the r2 relaxivity for magnetic iron oxide nanoparticles. The clustering methodology can be expanded also to other nanoparticle materials [CdSe/CdS/ZnS core/shell/shell quantum dots (QDs), CdSe/CdS quantum dots/quantum rods (QDQRs), gold nanoparticles, and mixtures thereof].

In situ functionalization and PEO coating of iron oxide nanocrystals using seeded emulsion polymerization.

Herein we demonstrate that seeded emulsion polymerization is a powerful tool to produce multiply functionalized PEO coated iron oxide nanocrystals. Advantageously, by simple addition of functional surfactants, functional monomers, or functional polymerizable linkers-solely or in combinations thereof-during the seeded emulsion polymerization process, a broad range of in situ functionalized polymer-coated iron oxide nanocrystals were obtained. This was demonstrated by purposeful modulation of the zeta potential of encapsulated iron oxide nanocrystals and conjugation of a dyestuff. Successful functionalization was unequivocally proven by TXRF. Furthermore, the spatial position of the functional groups can be controlled by choosing the appropriate spacers. In conclusion, this methodology is highly amenable for combinatorial strategies and will spur rapid expedited synthesis and purposeful optimization of a broad scope of nanocrystals.

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.

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.

Chemistry of Shape-Controlled Iron Oxide Nanocrystal Formation.

Herein, we demonstrate that meticulous and in-depth analysis of the reaction mechanisms of nanoparticle formation is rewarded by full control of the size, shape, and crystal structure of superparamagnetic iron oxide nanocrystals during synthesis. Starting from two iron sources, iron(II) and iron(III) carbonate, a strict separation of oleate formation from the generation of reactive pyrolysis products and concomitant nucleation of iron oxide nanoparticles was achieved. This protocol enabled us to analyze each step of nanoparticle formation independently in depth. The progress of the entire reaction was monitored via matrix-assisted laser desorption ionization time-of-flight mass spectrometry and gas chromatography, thus providing insight into the formation of various iron oleate species prior to nucleation. Interestingly, due to the intrinsic strongly reductive pyrolysis conditions of the oleate intermediates and redox process in early stages of the synthesis, pristine iron oxide nuclei were composed exclusively from wüstite irrespective of the oxidation state of the iron source. Controlling the reaction conditions provided a very broad range of size- and shape-defined monodispersed iron oxide nanoparticles. Curiously, after nucleation, star-shaped nanocrystals were obtained that underwent metamorphism toward cubic-shaped particles. Electron energy loss spectroscopy tomography revealed ex post oxidation of the primary wustite nanocrystal, providing a full 3D image of Fe2+ and Fe3+ distribution within. Overall, we developed a highly flexible synthesis, yielding multi-gram amounts of well-defined iron oxide nanocrystals of different sizes and morphologies.

Exceptionally strong, stiff and hard hybrid material based on an elastomer and isotropically shaped ceramic nanoparticles.

In this work the fabrication of hard, stiff and strong nanocomposites based on polybutadiene and iron oxide nanoparticles is presented. The nanocomposites are fabricated via a general concept for mechanically superior nanocomposites not based on the brick and mortar structure, thus on globular nanoparticles with nanosized organic shells. For the fabrication of the composites oleic acid functionalized iron oxide nanoparticles are decorated via ligand exchange with an α,ω-polybutadiene dicarboxylic acid. The functionalized particles were processed at 145 °C. Since polybutadiene contains double bonds the nanocomposites obtained a crosslinked structure which was enhanced by the presence of oxygen or sulfur. It was found that the crosslinking and filler percolation yields high elastic moduli of approximately 12-20 GPa and hardness of 15-18 GPa, although the polymer volume fraction is up to 40%. We attribute our results to a catalytically enhanced crosslinking reaction of the polymer chains induced by oxygen or sulfur and to the microstructure of the nanocomposite.

Nanocomposites of Highly Monodisperse Encapsulated Superparamagnetic Iron Oxide Nanocrystals Homogeneously Dispersed in a Poly(ethylene Oxide) Melt.

Nanocomposite materials based on highly stable encapsulated superparamagnetic iron oxide nanocrystals (SPIONs) were synthesized and characterized by scattering methods and transmission electron microscopy (TEM). The combination of advanced synthesis and encapsulation techniques using different diblock copolymers and the thiol-ene click reaction for cross-linking the polymeric shell results in uniform hybrid SPIONs homogeneously dispersed in a poly(ethylene oxide) matrix. Small-angle X-ray scattering and TEM investigations demonstrate the presence of mostly single particles and a negligible amount of dyads. Consequently, an efficient control over the encapsulation and synthetic conditions is of paramount importance to minimize the fraction of agglomerates and to obtain uniform hybrid nanomaterials.

Investigations of ion transport through nanoscale polymer membranes by fluorescence quenching of CdSe/CdS quantum dot/quantum rods.

Detailed steady-state and time-resolved fluorescence quenching measurements give deep insight into ion transport through nanometer thick diblock copolymer membranes, which were assembled as biocompatible shell material around CdSe/CdS quantum dot in quantum rods. We discuss the role of polymer chain length, intermolecular cross-linking and nanopore formation by analysing electron transfer processes from the photoexcited QDQRs to Cu(II) ions, which accumulate in the polymer membrane. Fluorescence investigations on single particle level additionally allow identifying ensemble inhomogeneities.

Controlling the physical and biological properties of highly fluorescent aqueous quantum dots using block copolymers of different size and shape.

The phase transfer of fluorescent CdSe based quantum dots (QDs) while retaining their properties and offering some advantages concerning the stability and functionalization characteristics is an important and intensively investigated field of research. Here we report how to tune and control the properties of CdSe/CdS/ZnS core-shell-shell QDs in water, using poly(isoprene-block-ethylene oxide) (PI-b-PEO) as a versatile system of amphiphilic diblock copolymers for the micellular encapsulation of nanoparticles (NPs). We show the synthesis of a novel PI-b-(PEO)2 miktoarm star polymer and how this different architecture besides the variation of the polymers' molecular weight gives us the opportunity to control the size of the built constructs in water between 24 and 53 nm. Because of this size control, an upper limit of the construct's diameter for the cellular uptake could be determined by a systemic study with human alveolar epithelial cells (A549) and murine macrophage leukemia cell (RAW-264.7). Furthermore, fluorescence quenching experiments with copper(II) and iron(III) ions show a strong influence of the used polymer on the shielding against these ions. This enables us to control the permeability of the polymer shell from very porous shells, which allow an almost complete cation exchange up to very dense shells. These even offer the possibility to perform copper(I) catalyzed click reactions while keeping the fluorescence of the QDs. All these results underline the huge variability and controllability of the PI-b-PEO diblock copolymer system for the encapsulation and functionalization of nanoparticles for biological applications. As a general trend, it can be stated that those coatings, which were most stable against quenchers, also showed the best resistivity with respect to unspecific cellular uptake.

A general route towards well-defined magneto- or fluorescent-plasmonic nanohybrids.

Herein, we present a general route towards defined nanohybrids, comprised of a fluorescent quantum dot (QD) or superparamagnetic iron oxide (Fe2O3) nanocrystal core and a tuneable corona of plasmonic gold or silver nanoparticles (NPs), adhered by a cross-linked poly(isoprene)-b-poly(ethylene glycol) diblock copolymer (PI-b-PEG) matrix. To this end, the PEG-terminus of the amphiphilic polymer was acylated with lipoic acid (LA), which, as is known, forms quasi-covalent Au-thiol- or Ag-thiol-bonds. Surprisingly, by variation of the ratio of the different NPs, inverse core/satellite structures bearing QDs or Fe2O3 around a metallic NP core were obtained. Furthermore, gold NPs or even closed gold shells were grown by in situ reductive deposition of Au(3+) ions on Fe2O3 NP seeds. Finally, in order to demonstrate the scope of the method, ternary nanohybrids, composed of QDs, Fe2O3 and Au NPs, were accomplished. All magneto-plasmonic and fluorescent-plasmonic materials were thoroughly characterized by absorption and emission spectroscopy, TEM and TEM-EDX. Antibody conjugation to these novel nanohybrids proved their practical utility in a prototype immunoassay.