Structural Study of the Photo-Mediated Growth of Silver Nanoprisms.

We present a small-angle X-ray scattering (SAXS) study of the anisotropic photoinduced growth of silver (Ag) nanoprisms in aqueous dispersions. The growth of nearly spherical (<10 nm) Ag particles into large (>40 nm) and thin (<10 nm) triangular nanoprisms induced by 550 nm laser is followed in terms of particle size using indirect and direct methods for irradiation times up to 150 min. During the process, the surface-to-volume ratio of the particles decreased. The SAXS data of the initial solution fit well to the model of polydisperse spheres with pronounced average diameters around 7.4 nm and 10 nm. The data after 45 min irradiation fit well to the model containing approximately the same amount of the initial particles and the end product, the nanoprisms.

Mutation-induced alterations of intra-filament subunit organization in vimentin filaments revealed by SAXS.

Vimentin intermediate filaments constitute a distinct filament system in mesenchymal cells that is instrumental for cellular mechanics and migration. In vitro, the rod-like monomers assemble in a multi-step, salt-dependent manner into micrometer long biopolymers. To disclose the underlying mechanisms further, we employed small angle X-ray scattering on two recombinant vimentin variants, whose assembly departs at strategic points from the normal assembly route: (i) vimentin with a tyrosine to leucine change at position 117; (ii) vimentin missing the non-α-helical carboxyl-terminal domain. Y117L vimentin assembles into unit-length filaments (ULFs) only, whereas ΔT vimentin assembles into filaments containing a higher number of tetramers per cross section than normal vimentin filaments. We show that the shape and inner structure of these mutant filaments is significantly altered. ULFs assembled from Y117L vimentin contain more, less tightly bundled vimentin tetramers, and ΔT vimentin filaments preserve the number density despite the higher number of tetramers per filament cross-section.

Structural and kinetic investigation of the hydride composite Ca(BH4)2 + MgH2 system doped with NbF5 for solid-state hydrogen storage.

Designing safe, compact and high capacity hydrogen storage systems is the key step towards introducing a pollutant free hydrogen technology into a broad field of applications. Due to the chemical bonds of hydrogen-metal atoms, metal hydrides provide high energy density in safe hydrogen storage media. Reactive hydride composites (RHCs) are a promising class of high capacity solid state hydrogen storage systems. Ca(BH4)2 + MgH2 with a hydrogen content of 8.4 wt% is one of the most promising members of the RHCs. However, its relatively high desorption temperature of ∼350 °C is a major drawback to meeting the requirements for practical application. In this work, by using NbF5 as an additive, the dehydrogenation temperature of this RHC was significantly decreased. To elucidate the role of NbF5 in enhancing the desorption properties of the Ca(BH4)2 + MgH2 (Ca-RHC), a comprehensive investigation was carried out via manometric measurements, mass spectrometry, Differential Scanning Calorimetry (DSC), in situ Synchrotron Radiation-Powder X-ray Diffraction (SR-PXD), X-ray Absorption Spectroscopy (XAS), Anomalous Small-Angle X-ray Scattering (ASAXS), Scanning and Transmission Electron Microscopy (SEM, TEM) and Nuclear Magnetic Resonance (NMR) techniques.

Impact of ion valency on the assembly of vimentin studied by quantitative small angle X-ray scattering.

The assembly kinetics of intermediate filament (IF) proteins from tetrameric complexes to single filaments and networks depends on the protein concentration, temperature and the ionic composition of their environment. We systematically investigate how changes in the concentration of monovalent potassium and divalent magnesium ions affect the internal organization of the resulting filaments. Small angle X-ray scattering (SAXS) is very sensitive to changes in the filament cross-section such as diameter or compactness. Our measurements reveal that filaments formed in the presence of magnesium chloride differ distinctly from filaments formed in the presence of potassium chloride. The principle multi-step assembly mechanism from tetramers via unit-length filaments (ULF) to elongated filaments is not changed by the valency of ions. However, the observed differences indicate that the magnesium ions free the head domains of tetramers from unproductive interactions to allow assembly but at the same time mediate strong inter-tetrameric interactions that impede longitudinal annealing of unit-length filaments considerably, thus slowing down filament growth.

Formation mechanism of silver nanoparticles stabilized in glassy matrices.

In any given matrix control over the final particle size distribution requires a constitutive understanding of the mechanisms and kinetics of the particle evolution. In this contribution we report on the formation mechanism of silver nanoparticles embedded in a soda-lime silicate glass matrix. For the silver ion-exchanged glass it is shown that at temperatures below 410 °C only molecular clusters (diameter <1 nm) are forming which are most likely silver dimers. These clusters grow to nanoparticles (diameter >1 nm) by annealing above this threshold temperature of 410 °C. It is evidenced that the growth and thus the final silver nanoparticle size are determined by matrix-assisted reduction mechanisms. As a consequence, particle growth proceeds after the initial formation of stable clusters by addition of silver monomers which diffuse from the glass matrix. This is in contrast to the widely accepted concept of particle growth in metal-glass systems, in which it is assumed that the nanoparticle formation is predominantly governed by Ostwald ripening processes.

Distribution of counterions around lignosulfonate macromolecules in different polar solvent mixtures.

Lignosulfonate is a colloidal polyelectrolyte that is obtained as a side product in sulfite pulping. In this work we wanted to study the noncovalent association of the colloids in different solvents, as well as to find out how the charged sulfonate groups are organized on the colloid surface. We studied sodium and rubidium lignosulfonate in water-methanol mixtures and in dimethyl formamide. The number average molecular weights of the Na- and Rb-lignosulfonate fractions were 7600 g/mol and 9100 g/mol, respectively, and the polydispersity index for both was 2. Anomalous small-angle X-ray scattering (ASAXS) was used for determining the distribution of counterions around the Rb-lignosulfonate macromolecules. The scattering curves were fitted with a model constructed from ellipsoids of revolution of different sizes. Counterions were taken into account by deriving an approximative formula for the scattering intensity of the Poisson-Boltzmann diffuse double layer model. The interaction term between the spheroidal particles was estimated using the local monodisperse approximation and the improved Hayter-Penfold structure factor given by the rescaled mean spherical approximation. Effective charge of the polyelectrolyte and the local dielectric constant of the solvent close to the globular polyelectrolyte were followed as a function of the methanol content in the solvent and lignosulfonate concentration. The lignosulfonate macromolecules were found to aggregate noncovalently in water-methanol mixtures with increasing methanol or lignosulfonate content in a specific directional manner. The flat macromolecule aggregates had a nearly constant thickness of 1-1.4 nm, while their diameter grew when counterion association onto the polyelectrolyte increased. These results indicate that the charged groups in lignosulfonate are mostly at the flat surfaces of the colloid, allowing the associated lignosulfonate complexes to grow further at the edges of the complex.

SAXS investigation of a cubic to a sponge (L3) phase transition in self-assembled lipid nanocarriers.

The encapsulation and release of peptides, proteins, nucleic acids, and drugs in nanostructured lipid carriers depend on the type of the self-assembled liquid-crystalline organization and the structural dimensions of the aqueous and membraneous compartments, which can be tuned by the multicomponent composition of the systems. In this work, small-angle X-ray scattering (SAXS) investigation is performed on the 'melting' transition of the bicontinuous double diamond cubic phase, formed by pure glycerol monooleate (MO), upon progressive inclusion of varying fractions of pharmaceutical-grade glycerol monooleate (GO) in the hydrated system. The self-assembled MO/GO mixtures are found to form diamond (Pn3m) inverted cubic, inverted hexagonal (H(II)), and sponge (L(3)) phases at ambient temperature in excess of aqueous medium without heat treatment. Mixing of the inverted-cubic-phase-forming MO and the sponge-phase-forming GO components, in equivalent proportions (50/50 w/w), yields an inverted hexagonal (H(II)) phase nanostructured carrier. Scattering models are applied for fitting of the experimental SAXS patterns and identification of the structural changes in the aqueous and lipid bilayer subcompartments. The possibility of transforming, at ambient temperature (20 °C), the bicontinuous cubic nanostructures into inverted hexagonal (H(II)) or sponge (L(3)) mesophases may facilitate novel biomedical applications of the investigated liquid crystalline self-assemblies.

A comprehensive study on lithium-based reactive hydride composite (Li-RHC) as a reversible solid-state hydrogen storage system toward potential mobile applications.

Reversible solid-state hydrogen storage is one of the key technologies toward pollutant-free and sustainable energy conversion. The composite system LiBH4-MgH2 can reversibly store hydrogen with a gravimetric capacity of 13 wt%. However, its dehydrogenation/hydrogenation kinetics is extremely sluggish (∼40 h) which hinders its usage for commercial applications. In this work, the kinetics of this composite system is significantly enhanced (∼96%) by adding a small amount of NbF5. The catalytic effect of NbF5 on the dehydrogenation/hydrogenation process of LiBH4-MgH2 is systematically investigated using a broad range of experimental techniques such as in situ synchrotron radiation X-ray powder diffraction (in situ SR-XPD), X-ray absorption spectroscopy (XAS), anomalous small angle X-ray scattering (ASAXS), and ultra/small-angle neutron scattering (USANS/SANS). The obtained results are utilized to develop a model that explains the catalytic function of NbF5 in hydrogen release and uptake in the LiBH4-MgH2 composite system.

Interactions of hydrophobin proteins in solution studied by small-angle X-ray scattering.

Hydrophobins are a group of very surface-active, fungal proteins known to self-assemble on various hydrophobic/hydrophilic interfaces. The self-assembled films coat fungal structures and mediate their attachment to surfaces. Hydrophobins are also soluble in water. Here, the association of hydrophobins HFBI and HFBII from Trichoderma reesei in aqueous solution was studied using small-angle x-ray scattering. Both HFBI and HFBII exist mainly as tetramers in solution in the concentration range 0.5-10 mg/ml. The assemblies of HFBII dissociate more easily than those of HFBI, which can tolerate changes of pH from 3 to 9 and temperatures in the range 5 degrees C-60 degrees C. The self-association of HFBI and HFBII is mainly driven by the hydrophobic effect, and addition of salts along the Hofmeister series promotes the formation of larger assemblies, whereas ethanol breaks the tetramers into monomers. The possibility that the oligomers in solution form the building blocks of the self-assembled film at the air/water interface is discussed.

Tailoring of the hierarchical structure within electrospun fibers due to supramolecular comb-coil block copolymers: polystyrene-block-poly(4-vinyl pyridine) plasticized by hydrogen bonded pentadecylphenol.

Previously we demonstrated hierarchical self-assembly and mesoporosity in electrospun fibers using selected polystyrene--poly(4-vinylpyridine) (PS--P4VP) diblock copolymers with hydrogen-bonded 3--pentadecylphenol (PDP), which rendered distorted spherical P4VP(PDP) domains within the PS matrix, internal lamellar order within the P4VP(PDP) domains, and allowed distorted spherical pores by removing PDP (. 2005, , 1048). Here we study whether the internal structure of electrospun fibers can be systematically tailored by varying the compositions of PS--P4VP(PDP). We expect these complexes to be feasible choices to combine electrospinning and self-assembly, as relatively high molecular weight block copolymers are useful for electrospinning, and enhanced structure formation due to plasticization by the amphiphilic PDP was expected. Not surprisingly, the self-assembled structures of the as-prepared fibers were less perfect than those in the corresponding well-annealed bulk materials. Compositions that show spherical self-assembly of P4VP(PDP) within the PS matrix in bulk lead to distinct and elongated worm-like P4VP(PDP) domains within the PS matrix in electrospun fibers. More symmetric compositions, which showed lamellar self-assembly in bulk, lead to structures where both PS and P4VP(PDP) domains were worm-like and elongated in a relatively symmetric manner. Finally, compositions which in bulk showed self-assembly of PS spheres within the P4VP(PDP) matrix, lead to separate distorted PS domains in the P4VP(PDP) matrix. Additionally, SAXS measurements suggest a lamellar structure within the P4VP(PDP) domains. As electrospinning is a facile method to prepare mesoscale fibers, and it is known that the amphiphiles can be removed from the hierarchical assemblies, the present method offers the potential to tune the internal porosity of the fibers for release and absorption purposes.

Yolk@Shell Nanoarchitectures with Bimetallic Nanocores-Synthesis and Electrocatalytic Applications.

In the present paper, we demonstrate a versatile approach for the one-pot synthesis of metal oxide yolk@shell nanostructures filled with bimetallic nanocores. This novel approach is based on the principles of hydrophobic nanoreactor soft-templating and is exemplified for the synthesis of various AgAuNP@tin-rich ITO (AgAu@ITOTR) yolk@shell nanomaterials. Hydrophobic nanoreactor soft-templating thereby takes advantage of polystyrene-block-poly(4-vinylpiridine) inverse micelles as two-compartment nanoreactor template, in which the core and the shell of the micelles serve as metal and metal oxide precursor reservoir, respectively. The composition, size and number of AuAg bimetallic nanoparticles incorporated within the ITOTR yolk@shell can easily be tuned. The conductivity of the ITOTR shell and the bimetallic composition of the AuAg nanoparticles, the as-synthesized AuAgNP@ITOTR yolk@shell materials could be used as efficient electrocatalysts for electrochemical glucose oxidation with improved onset potential when compared to their gold counterpart.

Large-scale parallel alignment of platelet-shaped particles through gravitational sedimentation.

Parallel and concentric alignment of microscopic building blocks into several orders of magnitude larger structures is commonly observed in nature. However, if similarly aligned structures are artificially produced their thickness is generally limited to just about one or two orders of magnitude more than the dimensions of the smallest element. We show that sedimentation provides a promising approach to manufacture solid materials consisting of well-aligned platelet-shaped particles while being more than 30,000 times thicker than the individual particle. Such sediments contain up to 28 vol% of particles without any further treatment and can be densified to 67 vol% particle fraction by subsequent unidirectional pressing. The degree of orientation of the platelet-shaped particles within the sediments was tracked by high-energy X-ray diffraction measurements. The Hermans orientation parameter, a statistical measure of the quality of alignment, was determined to be 0.63 ± 0.03 already for as-sedimented samples while the standard deviation of the orientation distribution of particles, another measure of average misalignment, was found to be (21.5 ± 1.4)°. After pressing, these values further improved to (0.81 ± 0.01) and (14.6 ± 0.4)°, respectively. Such quality of alignment competes with, if not even exceeds, values reported in the literature.

Turkevich in New Robes: Key Questions Answered for the Most Common Gold Nanoparticle Synthesis.

This contribution provides a comprehensive mechanistic picture of the gold nanoparticle synthesis by citrate reduction of HAuCl4, known as Turkevich method, by addressing five key questions. The synthesis leads to monodisperse final particles as a result of a seed-mediated growth mechanism. In the initial phase of the synthesis, seed particles are formed onto which the residual gold is distributed during the course of reaction. It is shown that this mechanism is a fortunate coincidence created by a favorable interplay of several chemical and physicochemical processes which initiate but also terminate the formation of seed particles and prevent the formation of further particles at later stages of reaction. Since no further particles are formed after seed particle formation, the number of seeds defines the final total particle number and therefore the final size. The gained understanding allows illustrating the influence of reaction conditions on the growth process and thus the final size distribution.

Synthesis and thermal stability of zirconia and yttria-stabilized zirconia microspheres.

HYPOTHESIS: Zirconia microparticles produced by sol-gel synthesis have great potential for photonic applications. To this end, identifying synthetic methods that yield reproducible control over size uniformity is important. Phase transformations during thermal cycling can disintegrate the particles. Therefore, understanding the parameters driving these transformations is essential for enabling high-temperature applications. Particle morphology is expected to influence particle processability and stability. Yttria-doping should improve the thermal stability of the particles, as it does in bulk zirconia. EXPERIMENTS: Zirconia and YSZ particles were synthesized by improved sol-gel approaches using fatty acid stabilizers. The particles were heated to 1500 °C, and structural and morphological changes were monitored by SEM, ex situ XRD and high-energy in situ XRD. FINDINGS: Zirconia particles (0.4-4.3 µm in diameter, 5-10% standard deviation) synthesized according to the modified sol-gel approaches yielded significantly improved monodispersities. As-synthesized amorphous particles transformed to the tetragonal phase at ∼450 °C with a volume decrease of up to ∼75% and then to monoclinic after heating from ∼650 to 850 °C. Submicron particles disintegrated at ∼850 °C and microparticles at ∼1200 °C due to grain growth. In situ XRD revealed that the transition from the amorphous to tetragonal phase was accompanied by relief in microstrain and the transition from tetragonal to monoclinic was correlated with the tetragonal grain size. Early crystallization and smaller initial grain sizes, which depend on the precursors used for particle synthesis, coincided with higher stability. Yttria-doping reduced grain growth, stabilized the tetragonal phase, and significantly improved the thermal stability of the particles.

Coaggregation of Two Anionic Azo Dyestuffs: A Combined Static Light Scattering and Small-Angle X-ray Scattering Study.

The formation of azo dyestuff aggregates in dilute aqueous solution induced by the addition of Mg2+, Ca2+, Sr2+, or Ba2+ ions is followed by time-resolved static light scattering (SLS) and time-resolved small-angle X-ray scattering (SAXS). Time-dependent molar mass data of the growing aggregates is interpreted by means of a kinetic model introduced by Lomakin et al. ( Proc. Natl. Acad. Sci. U.S.A. 1996 , 93 , 1125 ) for the description of ß-amyloid aggregation. This interpretation reveals significant trends within the homologous series of alkaline earth cations. The trends refer to the nucleation and the growth rate of the dyestuff fibers. Time-resolved SAXS experiments indicate that these first two stages are followed by a third one during which a network forms by partial lateral alignment of fibers. At high enough dyestuff concentrations, this network formation even leads to a gel-like phase. Anomalous SAXS (ASAXS) on such a gel phase formed upon the addition of Sr2+ revealed the extent of neutralization of the dyestuff molecules within the gel by the specifically interacting alkaline earth cations.

Block copolymer hollow fiber membranes with catalytic activity and pH-response.

We fabricated block copolymer hollow fiber membranes with self-assembled, shell-side, uniform pore structures. The fibers in these membranes combined pores able to respond to pH and acting as chemical gates that opened above pH 4, and catalytic activity, achieved by the incorporation of gold nanoparticles. We used a dry/wet spinning process to produce the asymmetric hollow fibers and determined the conditions under which the hollow fibers were optimized to create the desired pore morphology and the necessary mechanical stability. To induce ordered micelle assembly in the doped solution, we identified an ideal solvent mixture as confirmed by small-angle X-ray scattering. We then reduced p-nitrophenol with a gold-loaded fiber to confirm the catalytic performance of the membranes.

Structural diversity in iron oxide nanoparticle assemblies as directed by particle morphology and orientation.

The mesostructure of ordered arrays of anisotropic nanoparticles is controlled by a combination of packing constraints and interparticle interactions, two factors that are strongly dependent on the particle morphology. We have investigated how the degree of truncation of iron oxide nanocubes controls the mesostructure and particle orientation in drop cast mesocrystal arrays. The combination of grazing incidence small-angle X-ray scattering and scanning electron microscopy shows that mesocrystals of highly truncated cubic nanoparticles assemble in an fcc-type mesostructure, similar to arrays formed by iron oxide nanospheres, but with a significantly reduced packing density and displaying two different growth orientations. Strong satellite reflections in the GISAXS pattern indicate a commensurate mesoscopic superstructure that is related to stacking faults in mesocrystals of the anisotropic nanocubes. Our results show how subtle variation in shape anisotropy can induce oriented arrangements of nanoparticles of different structures and also create mesoscopic superstructures of larger periodicity.

Solution Small-Angle X-ray Scattering as a Screening and Predictive Tool in the Fabrication of Asymmetric Block Copolymer Membranes.

Small-angle X-ray scattering (SAXS) analysis of the diblock copolymer poly(styrene-b-(4-vinyl)pyridine) in a ternary solvent system of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide, and the triblock terpolymer poly(isoprene-b-styrene-b-(4-vinyl)pyridine) in a binary solvent system of 1,4-dioxane and tetrahydrofuran, reveals a concentration-dependent onset of ordered structure formation. Asymmetric membranes fabricated from casting solutions with polymer concentrations at or slightly below this ordering concentration possess selective layers with the desired nanostructure. In addition to rapidly screening possible polymer solution concentrations, solution SAXS analysis also predicts hexagonal and square pore lattices of the final membrane surface structure. These results suggest solution SAXS as a powerful tool for screening casting solution concentrations and predicting surface structure in the fabrication of asymmetric ultrafiltration membranes from self-assembled block copolymers.

Switchable pH-responsive polymeric membranes prepared via block copolymer micelle assembly.

A process is described to manufacture monodisperse asymmetric pH-responsive nanochannels with very high densities (pore density >2 × 10(14) pores per m(2)), reproducible in m(2) scale. Cylindric pores with diameters in the sub-10 nm range and lengths in the 400 nm range were formed by self-assembly of metal-block copolymer complexes and nonsolvent-induced phase separation. The film morphology was tailored by taking into account the stability constants for a series of metal-polymer complexes and confirmed by AFM. The distribution of metal-copolymer micelles was imaged by transmission electron microscopy tomography. The pH response of the polymer nanochannels is the strongest reported with synthetic pores in the nm range (reversible flux increase of more than 2 orders of magnitude when switching the pH from 2 to 8) and could be demonstrated by cryo-field emission scanning electron microscopy, SAXS, and ultra/nanofiltration experiments.

Long-living intermediates during a lamellar to a diamond-cubic lipid phase transition: a small-angle X-ray scattering investigation.

To generate nanostructured vehicles with tunable internal organization, the structural phase behavior of a self-assembled amphiphilic mixture involving poly(ethylene glycol) monooleate (MO-PEG) and glycerol monooleate (MO) is studied in excess aqueous medium by time-resolved small-angle X-ray scattering (SAXS) in the temperature range from 1 to 68 degrees C. The SAXS data indicate miscibility of the two components in lamellar and nonlamellar soft-matter nanostructures. The functionalization of the MO assemblies by a MO-PEG amphiphile, which has a flexible large hydrophilic moiety, appears to hinder the epitaxial growth of a double diamond (D) cubic lattice from the lamellar (L) bilayer structure during the thermal phase transition. The incorporated MO-PEG additive is found to facilitate the formation of structural intermediates. They exhibit greater characteristic spacings and large diffusive scattering in broad temperature and time intervals. Their features are compared with those of swollen long-living intermediates in MO/octylglucoside assemblies. A conclusion can be drawn that long-living intermediate states can be equilibrium stabilized in two- or multicomponent amphiphilic systems. Their role as cubic phase precursors is to smooth the structural distortions arising from curvature mismatch between flat and curved regions. The considered MO-PEG functionalized assemblies may be useful for preparation of sterically stabilized liquid-crystalline nanovehicles for confinement of therapeutic biomolecules.