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Surface chemistry and core defects are known to play a prominent role in governing the photophysical properties of nanocrystalline semiconductors. Nevertheless, investigating them in small nanocrystals remains a complex task. Here, by combining X-ray scattering techniques in the wide- and small-angle regions and using the Debye scattering equation (DSE) method of analysis, we unveil a high density of planar defects in oleate-terminated zincblende (ZB) CdSe colloidal quantum dots (QDs) and size-dependent faceting within a square-cuboid morphology. Atomistic models of faulted ZB nanocrystals, based on the probabilistic stacking of CdSe layers in cubic and hexagonal sequences, and data analysis point to the preferential location of faults near the center of nanocrystals. By finely modeling faulting and morphological effects on the X-ray scattering pattern, a relaxation of the Cd-Se bond distance parallel to the stacking direction, up to +3% (2.71 Å) with respect to the reference bulk value (2.63 Å), is detected, at the cubic/hexagonal transitions. The smallest nanocrystals show cubic {100} facets; {111} facets appear above 4 nm and progressively extend at larger sizes. These structural and morphological features likely vary depending on the synthesis conditions; nevertheless, since planar defects are nearly ubiquitous in CdSe QDs, the modeling approach here presented has a general validity. This work also points to the great potential of combining small- and wide-angle X-ray scattering and DSE-modeling techniques in gaining important knowledge on atomic-scale defects of semiconductor nanocrystals, underpinning the comprehension of the impact of structural defectiveness on the exciting properties of these QDs.

A variety of different tiles for the construction of DNA lattices have been developed since the structural DNA nanotechnology field was born. The majority of these are designed for the realization of close-packed structures, where DNA helices are arranged in parallel and tiles are connected through sticky ends. Assembly of such structures requires the use of cation-rich buffers to minimize repulsion between parallel helices, which poses limits to the application of DNA nanostructures. Wireframe structures, on the other hand, are less susceptible to salt concentration, but the assembly of wireframe lattices is limited by the availability of tiles and motifs. Herein, we report the construction of a polyhedral 12-arm junction for the self-assembly of wireframe DNA lattices. Our approach differs from traditional assembly of DNA tiles through hybridization of sticky ends. Instead, the assembly approach presented here uses small polyhedral shapes as connecting points and branch points of wires in a lattice structure. Using this design principle and characterization techniques, such as transmission electron microscopy, single-particle reconstruction, patterning of gold nanoparticles, dynamic light scattering, UV melting analyses, and small-angle X-ray scattering among others, we demonstrated formation of finite 12-way junction structures, as well as 1D and 2D short assemblies, demonstrating an alternative way of designing polyhedral structures and lattices.

Crystal defects in highy luminescent colloidal nanocrystals (NCs) of CsPbX 3 perovskites (X = Cl, Br, I) are investigated. Here, using X-ray total scattering techniques and the Debye scattering equation (DSE), we provide evidence that the local structure of these NCs always exhibits orthorhombic tilting of PbX 6 octahedra within locally ordered subdomains. These subdomains are hinged through a two-/three-dimensional (2D/3D) network of twin boundaries through which the coherent arrangement of the Pb ions throughout the whole NC is preserved. The density of these twin boundaries determines the size of the subdomains and results in an apparent higher-symmetry structure on average in the high-temperature modification. Dynamic cooperative rotations of PbX 6 octahedra are likely at work at the twin boundaries, causing the rearrangement of the 2D or 3D network, particularly effective in the pseudocubic phases. An orthorhombic, 3D γ-phase, isostructural to that of CsPbBr 3 is found here in as-synthesized CsPbI 3 NCs.

Atherosclerosis and its clinical consequences are the leading cause of death in the western hemisphere. While many studies throughout the last decades have aimed at understanding the disease, the clinical markers in use today still fail to accurately predict the risks. The role of the current main clinical indicator, low density lipoprotein (LDL), in depositing fat to the vessel wall is believed to be the onset of the process. However, many subfractions of the LDL, which differ both in structure and composition, are present in the blood and among different individuals. Understanding the relationship between LDL structure and composition is key to unravel the specific role of various LDL components in the development and/or prevention of atherosclerosis. Here, we describe a model for analyzing small-angle X-ray scattering data for rapid and robust structure determination for the LDL. The model not only gives the overall structure but also the particular internal layering of the fats inside the LDL core. Thus, the melting of the LDL can be followed in situ as a function of temperature for samples extracted from healthy human patients and purified using a double protocol based on ultracentrifugation and size-exclusion chromatography. The model provides information on: (i) the particle-specific melting temperature of the core lipids, (ii) the structural organization of the core fats inside the LDL, (iii) the overall shape of the particle, and (iv) the flexibility and overall conformation of the outer protein/hydrophilic layer at a given temperature as governed by the organization of the core. The advantage of this method over other techniques such as cryo-TEM is the possibility of in situ experiments under near-physiological conditions which can be performed relatively fast (minutes at home source, seconds at synchrotron). This approach now allows the monitoring of structural changes in the LDL upon different stresses from the environment, such as changes in temperature, oxidation, or external agents used or currently in development against atherosclerotic plaque build-up and which are targeting the LDL.

The electrokinetic energy conversion (EKEC) of hydraulic work directly into electrical energy has been investigated in charged polymeric membranes with different pore charge densities and characteristic diameters of the nanoporous network. The membranes were synthesized from blends of nitrocellulose and sulfonated polystyrene (SPS) and were comprehensively characterized with respect to structure, composition, and transport properties. It is shown that the SPS can be used as a sacrificial pore generation medium to tune the pore size and membrane porosity, which in turn highly affects the transport properties of the membranes. Furthermore, it is shown that very high EKEC efficiencies (>35%) are encountered in a rather narrow window of the properties of the nanoporous membrane network, that is, with pore diameters of ca. 10 nm and pore charge densities of 4.6 × 10(2) to 1.5 × 10(3) mol SO3(-) m(-3) for dilute solutions (0.03 M LiCl). The high absolute value of the efficiency combined with the determination of the optimal membrane morphology makes membrane-based EKEC devices a step closer to practical applications and high-performance membrane design less empirical.

The assembly, structure, and stability of DNA nanocages with the shape of truncated octahedra have been studied. The cages are composed of 12 double-stranded B-DNA helices interrupted by single-stranded linkers of thymidines of varying length that constitute the truncated corners of the structure. The structures assemble with a high efficiency in a one-step procedure, compared to previously published structures of similar complexity. The structures of the cages were determined by small-angle X-ray scattering. With increasing linker length, there is a systematic increase of the cage size and decrease of the twist angle of the double helices with respect to the symmetry planes of the cage structure. In the present study, we demonstrate the length of the single-stranded linker regions, which impose a certain degree of flexibility to the structure, to be the important determinant for efficient assembly. The linker length can be decreased to three thymidines without affecting assembly yield or the overall structural characteristics of the DNA cages. A linker length of two thymidines represents a sharp cutoff abolishing cage assembly. This is supported by energy minimization calculations suggesting substantial hydrogen bond deformation in a cage with linkers of two thymidines.

A DNA nanocage has been recently characterized by small-angle X-ray scattering (SAXS) and cryo-transmission electron microscopy as a DNA octahedron having a central cavity larger than the apertures in the surrounding DNA lattice. Starting from the SAXS data, a DNA nanocage has been modeled and simulated by classical molecular dynamics to evaluate in silico its structural properties and stability. Global properties, principal component analysis, and DNA geometrical parameters, calculated along the entire trajectory, indicate that the cage is stable and that the B-DNA conformation, also if slightly distorted, is maintained for all the simulation time. Starting from the initial model, the nanocage scaffold undergoes a contraction of the thymidine strands, connecting the DNA double helices, suggesting that the length of the thymidine strands is a crucial aspect in the modulation of the nanocage stability. A comparison of the average structure as obtained from the simulation shows good agreement with the SAXS experimental data.

Nanocrystalline ZrO(2) samples with narrow size distributions and mean particle sizes below 10 nm have been synthesized in a continuous flow reactor in near and supercritical water as well as supercritical isopropyl alcohol using a wide range of temperatures, pressures, concentrations and precursors. The samples were comprehensively characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS), and the influence of the synthesis parameters on the particle size, particle size distribution, shape, aggregation and crystallinity was studied. On the basis of the choice of synthesis parameters either monoclinic or tetragonal zirconia phases can be obtained. The results suggest a critical particle size of 5-6 nm for nanocrystalline monoclinic ZrO(2) under the present conditions, which is smaller than estimates reported in the literature. Thus, very small monoclinic ZrO(2) particles can be obtained using a continuous flow reactor. This is an important result with respect to improvement of the catalytic properties of nanocrystalline ZrO(2).