Ordered three-dimensional nanomaterials using DNA-prescribed and valence-controlled material voxels.

The ability to organize nanoscale objects into well-defined three-dimensional (3D) arrays can translate advances in nanoscale synthesis into targeted material fabrication. Despite successes in nanoparticle assembly, most extant methods are system specific and not fully compatible with biomolecules. Here, we report a platform for creating distinct 3D ordered arrays from different nanomaterials using DNA-prescribed and valence-controlled material voxels. These material voxels consist of 3D DNA frames that integrate nano-objects within their scaffold, thus enabling the object's valence and coordination to be determined by the frame's vertices, which can bind to each other through hybridization. Such DNA material voxels define the lattice symmetry through the spatially prescribed valence decoupling the 3D assembly process from the nature of the nanocomponents, such as their intrinsic properties and shapes. We show this by assembling metallic and semiconductor nanoparticles and also protein superlattices. We support the technological potential of such an assembly approach by fabricating light-emitting 3D arrays with diffraction-limited spectral purity and 3D enzymatic arrays with increased activity.

Nanoscale viscosity of confined polyethylene oxide.

Complex fluids near interfaces or confined within nanoscale volumes can exhibit substantial shifts in physical properties compared to bulk, including glass transition temperature, phase separation, and crystallization. Because studies of these effects typically use thin film samples with one dimension of confinement, it is generally unclear how more extreme spatial confinement may influence these properties. In this work, we used x-ray photon correlation spectroscopy and gold nanoprobes to characterize polyethylene oxide confined by nanostructured gratings (<100nm width) and measured the viscosity in this nanoconfinement regime to be ∼500 times the bulk viscosity. This enhanced viscosity occurs even when the scale of confinement is several times the polymer's radius of gyration, consistent with previous reports of polymer viscosity near flat interfaces.

Coherent amplification of X-ray scattering from meso-structures.

Small-angle X-ray scattering (SAXS) often includes an unwanted background, which increases the required measurement time to resolve the sample structure. This is undesirable in all experiments, and may make measurement of dynamic or radiation-sensitive samples impossible. Here, we demonstrate a new technique, applicable when the scattering signal is background-dominated, which reduces the requisite exposure time. Our method consists of exploiting coherent interference between a sample with a designed strongly scattering 'amplifier'. A modified angular correlation function is used to extract the symmetry of the interference term; that is, the scattering arising from the interference between the amplifier and the sample. This enables reconstruction of the sample's symmetry, despite the sample scattering itself being well below the intensity of background scattering. Thus, coherent amplification is used to generate a strong scattering term (well above background), from which sample scattering is inferred. We validate this method using lithographically defined test samples.

Healing X-ray scattering images.

X-ray scattering images contain numerous gaps and defects arising from detector limitations and experimental configuration. We present a method to heal X-ray scattering images, filling gaps in the data and removing defects in a physically meaningful manner. Unlike generic inpainting methods, this method is closely tuned to the expected structure of reciprocal-space data. In particular, we exploit statistical tests and symmetry analysis to identify the structure of an image; we then copy, average and interpolate measured data into gaps in a way that respects the identified structure and symmetry. Importantly, the underlying analysis methods provide useful characterization of structures present in the image, including the identification of diffuse versus sharp features, anisotropy and symmetry. The presented method leverages known characteristics of reciprocal space, enabling physically reasonable reconstruction even with large image gaps. The method will correspondingly fail for images that violate these underlying assumptions. The method assumes point symmetry and is thus applicable to small-angle X-ray scattering (SAXS) data, but only to a subset of wide-angle data. Our method succeeds in filling gaps and healing defects in experimental images, including extending data beyond the original detector borders.

Supra-Nanoparticle Functional Assemblies through Programmable Stacking.

The quest for the by-design assembly of material and devices from nanoscale inorganic components is well recognized. Conventional self-assembly is often limited in its ability to control material morphology and structure simultaneously. Here, we report a general method of assembling nanoparticles in a linear "pillar" morphology with regulated internal configurations. Our approach is inspired by supramolecular systems, where intermolecular stacking guides the assembly process to form diverse linear morphologies. Programmable stacking interactions were realized through incorporation of DNA coded recognition between the designed planar nanoparticle clusters. This resulted in the formation of multilayered pillar architectures with a well-defined internal nanoparticle organization. By controlling the number, position, size, and composition of the nanoparticles in each layer, a broad range of nanoparticle pillars were assembled and characterized in detail. In addition, we demonstrated the utility of this stacking assembly strategy for investigating plasmonic and electrical transport properties.

Velocity measurement by coherent x-ray heterodyning.

We present a small-angle coherent x-ray scattering technique used for measuring flow velocities in slow moving materials. The technique is an extension of X-ray Photon Correlation Spectroscopy (XPCS): It involves mixing the scattering from moving tracer particles with a static reference that heterodynes the signal. This acts to elongate temporal effects caused by flow in homodyne measurements, allowing for a more robust measurement of flow properties. Using coherent x-ray heterodyning, velocities ranging from 0.1 to 10 µm/s were measured for a viscous fluid pushed through a rectangular channel. We describe experimental protocols and theory for making these Poiseuille flow profile measurements and also develop the relevant theory for using heterodyne XPCS to measure velocities in uniform and Couette flows.

Reversible Nanoparticle Cubic Lattices in Blue Phase Liquid Crystals.

Blue phases (BPs), a distinct class of liquid crystals (LCs) with 3D periodic ordering of double twist cylinders involving orthogonal helical director twists, have been theoretically studied as potential templates for tunable colloidal crystals. Here, we report the spontaneous formation of thermally reversible, cubic crystal nanoparticle (NP) assemblies in BPs. Gold NPs, functionalized to be highly miscible in cyanobiphenyl-based LCs, were dispersed in BP mixtures and characterized by polarized optical microscopy and synchrotron small-angle X-ray scattering (SAXS). The NPs assemble by selectively migrating to periodic strong trapping sites in the BP disclination lines. The NP lattice, remarkably robust given the small particle size (4.5 nm diameter), is commensurate with that of the BP matrix. At the BP I to BP II phase transition, the NP lattice reversibly switches between two different cubic structures. The simultaneous presence of two different symmetries in a single material presents an interesting opportunity to develop novel dynamic optical materials.