Nanoparticle-induced morphological transformation in block copolymer-based nanocomposites.

By controlling the chemical composition and the spatial organization of nanoparticles, hybrid nanocomposites incorporating ordered arrangements of nanoparticles could be endowed with exotic physical and chemical properties to fulfill demands in advanced electronics or energy-harvesting devices. However, a simple method to fabricate hybrid nanocomposites with precise control of nanoparticle distribution is still challenging. We demonstrate that block copolymer-based nanocomposites containing well-ordered nanoparticles with various morphologies can be readily obtained by adjusting the nanoparticle concentration. Moreover, the structural evolution of nanocomposite thin films as a function of nanoparticle loading is unveiled using grazing-incidence transmission small-angle X-ray scattering and atomic force microscopy. The morphological transformation proceeds through a phase transition from perforated lamellae to in-plane cylinder layout, followed by structural changes. The successful achievement of a variety of morphologies represents an effective and straightforward approach to producing functional hybrid nanocomposites for potential applications in various functional devices.

Self-Assembly of All-DNA Rods with Controlled Patchiness.

Double-stranded DNA (dsDNA) fragments exhibit noncovalent attractive interactions between their tips. It is still unclear how DNA liquid crystal self-assembly is affected by such blunt-end attractions. It is demonstrated that stiff dsDNA fragments with moderate aspect ratio can specifically self-assemble in concentrated aqueous solutions into different types of smectic mesophases on the basis of selectively screening of blunt-end DNA stacking interactions. To this end, this type of attractions are engineered at the molecular level by constructing DNA duplexes where the attractions between one or both ends are screened by short hairpin caps. All-DNA bilayer and monolayer smectic-A type of phases, as well as a columnar phase, can be stabilized by controlling attractions strength. The results imply that the so far elusive smectic-A in DNA rod-like liquid crystals is a thermodynamically stable phase. The existence of the bilayer smectic phase is confirmed by Monte-Carlo simulations of hard cylinders decorated with one attractive terminal site. This work demonstrates that DNA blunt-ends behave as well-defined monovalent attractive patches whose strength and position can be potentially precisely tuned, highlighting unique opportunities concerning the stabilization of nonconventional DNA-based lyotropic liquid crystal phases assembled by all-DNA patchy particles with arbitrary geometry and composition.

Self assembling cluster crystals from DNA based dendritic nanostructures.

Cluster crystals are periodic structures with lattice sites occupied by several, overlapping building blocks, featuring fluctuating site occupancy, whose expectation value depends on thermodynamic conditions. Their assembly from atomic or mesoscopic units is long-sought-after, but its experimental realization still remains elusive. Here, we show the existence of well-controlled soft matter cluster crystals. We fabricate dendritic-linear-dendritic triblock composed of a thermosensitive water-soluble polymer and nanometer-scale all-DNA dendrons of the first and second generation. Conclusive small-angle X-ray scattering (SAXS) evidence reveals that solutions of these triblock at sufficiently high concentrations undergo a reversible phase transition from a cluster fluid to a body-centered cubic (BCC) cluster crystal with density-independent lattice spacing, through alteration of temperature. Moreover, a rich concentration-temperature phase diagram demonstrates the emergence of various ordered nanostructures, including BCC cluster crystals, birefringent cluster crystals, as well as hexagonal phases and cluster glass-like kinetically arrested states at high densities.

Unravelling Magnetic Nanochain Formation in Dispersion for In Vivo Applications.

Self-assembly of iron oxide nanoparticles (IONPs) into 1D chains is appealing, because of their biocompatibility and higher mobility compared to 2D/3D assemblies while traversing the circulatory passages and blood vessels for in vivo biomedical applications. In this work, parameters such as size, concentration, composition, and magnetic field, responsible for chain formation of IONPs in a dispersion as opposed to spatially confining substrates, are examined. In particular, the monodisperse 27 nm IONPs synthesized by an extended LaMer mechanism are shown to form chains at 4 mT, which are lengthened with applied field reaching 270 nm at 2.2 T. The chain lengths are completely reversible in field. Using a combination of scattering methods and reverse Monte Carlo simulations the formation of chains is directly visualized. The visualization of real-space IONPs assemblies formed in dispersions presents a novel tool for biomedical researchers. This allows for rapid exploration of the behavior of IONPs in solution in a broad parameter space and unambiguous extraction of ​the parameters of the equilibrium structures. Additionally, it can be extended to study novel assemblies formed by more complex geometries of IONPs.

Mechanism of magnetization reduction in iron oxide nanoparticles.

Iron oxide nanoparticles are presently considered as main work horses for various applications including targeted drug delivery and magnetic hyperthermia. Several questions remain unsolved regarding the effect of size onto their overall magnetic behavior. One aspect is the reduction of magnetization compared to bulk samples. A detailed understanding of the underlying mechanisms of this reduction could improve the particle performance in applications. Here we use a number of complementary experimental techniques including neutron scattering and synchrotron X-ray diffraction to arrive at a consistent conclusion. We confirm the observation from previous studies of a reduced saturation magnetization and argue that this reduction is mainly associated with the presence of antiphase boundaries, which are observed directly using high-resolution transmission electron microscopy and indirectly via an anisotropic peak broadening in X-ray diffraction patterns. Additionally small-angle neutron scattering with polarized neutrons revealed a small non-magnetic surface layer, that is, however, not sufficient to explain the observed loss in magnetization alone.

DNA Self-Assembly Mediated by Programmable Soft-Patchy Interactions.

Adding shape and interaction anisotropy to a colloidal particle offers exquisitely tunable routes to engineer a rich assortment of complex-architected structures. Inspired by the hierarchical self-assembly concept with block copolymers and DNA liquid crystals and exploiting the unique assembly properties of DNA, we report here the construction and self-assembly of DNA-based soft-patchy anisotropic particles with a high degree of modularity in the system's design. By programmable positioning of thermoresponsive polymeric patches on the backbone of a stiff DNA duplex with linear and star-shaped architecture, we reversibly drive the DNA from a disordered ensemble to a diverse array of long-range ordered multidimensional nanostructures with tunable lattice spacing, ranging from lamellar to bicontinuous double-gyroid and double-diamond cubic morphologies, through the alteration of temperature. Our results demonstrate that the proposed hierarchical self-assembly strategy can be applied to any kind of DNA nanoarchitecture, highlighting the design principles for integration of self-assembly concepts from the physics of liquid crystals, block copolymers, and patchy colloids into the continuously growing interdisciplinary research field of structural DNA nanotechnology.

Strong size selectivity in the self-assembly of rounded nanocubes into 3D mesocrystals.

The self-assembly of nanoparticles into highly ordered crystals is largely influenced by variations in the size and shape of the constituent particles, with crystallization generally not observed if their polydispersity is too large. Here, we report on size selectivity in the self-assembly of rounded cubic maghemite nanoparticles into three-dimensional mesocrystals. Different X-ray scattering techniques are used to study and compare a nanoparticle dispersion that is used later for self-assembly, an ensemble of mesocrystals grown on a substrate, as well as an individual mesocrystal. The individual µm-sized mesocrystal is isolated using a focused-ion-beam-based technique and investigated by the diffraction of a micro-focused X-ray beam. Structural analysis reveals that individual mesocrystals have a drastically smaller size dispersity of nanoparticles than that in the initial dispersion, implying very strong size selectivity during self-assembly. The small size dispersity of the nanoparticles within individual mesocrystals is accompanied by a very narrow lattice parameter distribution. In contrast, the lattice parameter distribution within all mesocrystals of an ensemble is about four times wider than that of individual mesocrystals, indicating significant size fractionalization between mesocrystals during self-assembly. The small size dispersity within each mesocrystal has important implications for their physical properties.

Self assembled monolayer of silica nanoparticles with improved order by drop casting.

This paper reports on the formation of large area, self assembled, highly ordered monolayers of stearyl alcohol grafted silica nanospheres of ≈50 nm diameter on a silicon substrate based on the drop-casting method. Our novel approach to achieve improved order uses stearyl alcohol as an assistant by adding it to the colloidal NanoParticle (NP) dispersion from which the monolayers are formed. Additionally, a heat treatment step is added, to melt the stearyl alcohol in the monolayer and thereby give the particles more time to further self-assemble, leading to additional improvement in the monolayer quality. The formation of the monolayers is significantly affected by the concentration of the NPs and the stearyl alcohol, the volume of the drop as well as the time of the heat treatment. A high surface coverage and uniform monolayer film of SiO2 NPs is achieved by appropriate control of the above-mentioned preparation parameters. Structural characterization of the obtained SiO2 NP monolayer was done locally by Scanning Electron Microscopy (SEM), and globally by X-ray reflectivity (XRR) and grazing incidence small-angle X-ray scattering (GISAXS), where the data was reproduced by simulation within the Distorted Wave Born Approximation (DWBA). In conclusion, our modified drop-casting method is a simple, inexpensive method, which provides highly ordered self-assembled monolayers of silica particles, if combined with a compatible additive and a heat treatment step. This method might be more general and also applicable to different particles after finding an appropriate additive.

Manipulation of dipolar magnetism in low-dimensional iron oxide nanoparticle assemblies.

The manipulation of magnetic states in nanoparticle supercrystals promises new pathways to design nanocrystalline magnetic materials and devices. Trench-patterned silicon substrates were used as templates to guide the self-assembly of iron oxide nanoparticles. Grazing incidence small angle X-ray scattering shows that the nanoparticles form a long-range ordered structure along the trench direction while in the direction perpendicular to the trenches, no coherent structure is observable. Electron holography provides evidence of an ordered magnetic state of nanoparticle moments in the remanent state after the application of a saturation magnetic field parallel to the trenches. However, a disordered magnetic state was observed in a perpendicular geometry. Hysteresis loops indicate that the nanoparticle moments form a superferromagnetic state for the geometry parallel to the trenches. Memory effect investigations reveal that the disordered magnetic state corresponds to a collective superspin glass state in the perpendicular geometry, while the superferromagnetic state in the parallel geometry suppresses the superspin glass state.

Reversible Control of Physical Properties via an Oxygen-Vacancy-Driven Topotactic Transition in Epitaxial La0.7 Sr0.3 MnO3- δ Thin Films.

The vacancy distribution of oxygen and its dynamics directly affect the functional response of complex oxides and their potential applications. Dynamic control of the oxygen composition may provide the possibility to deterministically tune the physical properties and establish a comprehensive understanding of the structure-property relationship in such systems. Here, an oxygen-vacancy-induced topotactic transition from perovskite to brownmillerite and vice versa in epitaxial La0.7 Sr0.3 MnO3- δ thin films is identified by real-time X-ray diffraction. A novel intermediate phase with a noncentered crystal structure is observed for the first time during the topotactic phase conversion which indicates a distinctive transition route. Polarized neutron reflectometry confirms an oxygen-deficient interfacial layer with drastically reduced nuclear scattering length density, further enabling a quantitative determination of the oxygen stoichiometry (La0.7 Sr0.3 MnO2.65 ) for the intermediate state. Associated physical properties of distinct topotactic phases (i.e., ferromagnetic metal and antiferromagnetic insulator) can be reversibly switched by an oxygen desorption/absorption cycling process. Importantly, a significant lowering of necessary conditions (temperatures below 100 °C and conversion time less than 30 min) for the oxygen reloading process is found. These results demonstrate the potential applications of defect engineering in the design of perovskite-based functional materials.

The high-intensity reflectometer of the Jülich Centre for Neutron Science: MARIA.

MARIA (magnetism reflectometer with high incident angle) is a world class vertical sample reflectometer dedicated to the investigation of thin films in the fields of magnetism, soft matter and biology. The elliptical vertically focusing guide allows one to measure small samples with a typical size of 1 × 1 cm very efficiently. The double-bounce polarizer and the in situ pumped 3He SEOP (spin-exchange optical pumping) neutron spin filter cell for analysing the polarization of the reflected neutron beam can be moved into the beam in seconds. The polarized flux of MARIA amounts to 5 × 107 n (s cm2)-1 at the sample position with a horizontally collimated beam of 3 mrad, a wavelength of λ = 4.5 Šand a wavelength resolution of Δλ/λ = 10%. In the non-polarized mode a flux of 1.2 × 108 n (s cm2)-1 is achieved in this configuration. MARIA is also capable of grazing-incidence small-angle neutron scattering measurements, using a pinhole collimation with two four-segment slits and an absorber that prevents the focusing of the elliptical guide in the vertical direction.

Superlattice growth and rearrangement during evaporation-induced nanoparticle self-assembly.

Understanding the assembly of nanoparticles into superlattices with well-defined morphology and structure is technologically important but challenging as it requires novel combinations of in-situ methods with suitable spatial and temporal resolution. In this study, we have followed evaporation-induced assembly during drop casting of superparamagnetic, oleate-capped γ-Fe2O3 nanospheres dispersed in toluene in real time with Grazing Incidence Small Angle X-ray Scattering (GISAXS) in combination with droplet height measurements and direct observation of the dispersion. The scattering data was evaluated with a novel method that yielded time-dependent information of the relative ratio of ordered (coherent) and disordered particles (incoherent scattering intensities), superlattice tilt angles, lattice constants, and lattice constant distributions. We find that the onset of superlattice growth in the drying drop is associated with the movement of a drying front across the surface of the droplet. We couple the rapid formation of large, highly ordered superlattices to the capillary-induced fluid flow. Further evaporation of interstitital solvent results in a slow contraction of the superlattice. The distribution of lattice parameters and tilt angles was significantly larger for superlattices prepared by fast evaporation compared to slow evaporation of the solvent.

Tuning the structure and habit of iron oxide mesocrystals.

A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on iron oxide nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and the quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6-12.6 nm) are isostructural with a body centred tetragonal (bct) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic iron oxide nanocube mesocrystals based on nanocube edge length and magnetic field strength.