Iron coordination in liquid FeAl2O4.

The structure of aerodynamically levitated liquid [Formula: see text] was measured by neutron diffraction with isotope substitution (NDIS). Classical and ab initio molecular dynamics simulations were performed and their results were found to be in close agreement with each other and the NDIS data. The results reveal that molten [Formula: see text] may be considered as an ionic liquid without any preference for particular short-range structural motifs. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

Effect of acoustic standing waves on cellular viability and metabolic activity.

Acoustic standing wave devices offer excellent potential applications in biological sciences for drug delivery, cell manipulation and tissue engineering. However, concerns have been raised about possible destructive effects on cells due to the applied acoustic field, in addition to other produced secondary factors. Here, we report a systematic study employing a 1D resonant acoustic trapping device to evaluate the cell viability and cell metabolism for a healthy cell line (Human Dermal Fibroblasts, HDF) and a cervical cancer cell line (HeLa), as a function of time and voltages applied (4-10 Vpp) under temperature-controlled conditions. We demonstrate that high cell viability can be achieved reliably when the device is operated at its minimum trapping voltage and tuned carefully to maximise the acoustic standing wave field at the cavity resonance. We found that cell viability and reductive metabolism for both cell lines are kept close to control levels at room temperature and at 34 °C after 15 minutes of acoustic exposure, while shorter acoustic exposures and small changes on temperature and voltages, had detrimental effects on cells. Our study highlights the importance of developing robust acoustic protocols where the operating mode of the acoustic device is well defined, characterized and its temperature carefully controlled, for the application of acoustic standing waves when using live cells and for potential clinical applications.

Fabrication of Micropatterned Dipeptide Hydrogels by Acoustic Trapping of Stimulus-Responsive Coacervate Droplets.

Acoustic standing waves offer an excellent opportunity to trap and spatially manipulate colloidal objects. This noncontact technique is used for the in situ formation and patterning in aqueous solution of 1D or 2D arrays of pH-responsive coacervate microdroplets comprising poly(diallyldimethylammonium) chloride and the dipeptide N-fluorenyl-9-methoxy-carbonyl-D-alanine-D-alanine. Decreasing the pH of the preformed droplet arrays results in dipeptide nanofilament self-assembly and subsequent formation of a micropatterned supramolecular hydrogel that can be removed as a self-supporting monolith. Guest molecules such as molecular dyes, proteins, and oligonucleotides are sequestered specifically within the coacervate droplets during acoustic processing to produce micropatterned hydrogels containing spatially organized functional components. Using this strategy, the site-specific isolation of multiple enzymes to drive a catalytic cascade within the micropatterned hydrogel films is exploited.

Establishing the structure of GeS(2) at high pressures and temperatures: a combined approach using x-ray and neutron diffraction.

The change in structure of glassy GeS(2) with pressure increasing to [Formula: see text] at ambient temperature was explored by using in situ neutron and x-ray diffraction. Under ambient conditions, the glass structure is made from a mixture of corner- and edge-sharing Ge(S(1/2))(4) tetrahedra where 47(5)% of the Ge atoms are involved in edge-sharing configurations. The network formed by these tetrahedra orders on an intermediate range as manifested by the appearance of a pronounced first sharp diffraction peak in the measured total structure factors at a scattering vector k = 1.02(2) Å(-1) which has a large contribution from Ge-Ge correlations. The intermediate range order breaks down when the pressure on the glass increases above ≈2 GPa but there does not appear to be a significant alteration of the Ge-S coordination number or corresponding bond length with increasing density. The results for the glass are consistent with a densification mechanism in which there is a replacement of edge-sharing by corner-sharing Ge centred tetrahedral motifs and/or a reduction in the Ge-[Formula: see text]-Ge bond angle between corner-sharing tetrahedral motifs with increasing pressure. The change in structure with increasing temperature at a pressure of [Formula: see text] was also investigated by means of in situ x-ray diffraction as the glass crystallized and then liquefied. At 5.2(1) GPa and 828(50) K the system forms a tetragonal crystal, with space group [Formula: see text] and cell parameters a = b = 4.97704(12) and c = 9.5355(4) Å, wherein corner-sharing Ge(S(1/2))(4) tetrahedra pack to form a dense three-dimensional network. A method is described for correcting x-ray diffraction data taken in situ under high pressure, high temperature conditions for a cylindrical sample, container and gasket geometry with a parallel incident beam and with a scattered beam that is defined using an oscillating radial collimator. A method is also outlined for obtaining coordination numbers from direct integration of the peaks in measured x-ray total pair distribution functions.

Liquid-liquid phase transition in supercooled yttria-alumina.

The structure and thermal characteristics of aerodynamically levitated samples of yttria-alumina in the liquid, supercooled liquid and solid phases were explored in an extensive series of high energy x-ray diffraction, small angle neutron scattering, and pyrometric cooling measurements. Particular focus was placed on the compound (Y2O3)(x)(Al2O3)(1-x) with x = 0.2 for which a liquid-liquid phase transition at a temperature of 1788 K has recently been reported. No structural or thermal signature in support of this metastable phase transition could be found.

Phase separation, crystallization and polyamorphism in the Y(2)O(3)-Al(2)O(3) system.

A detailed study of glass formation from aerodynamically levitated liquids in the (Y(2)O(3))(x)(Al(2)O(3))(1-x) system for the composition range 0.21≤x≤0.41 was undertaken by using pyrometric, optical imaging and x-ray diffraction methods. Homogeneous and clear single-phase glasses were produced over the composition range [Formula: see text]. For Y(2)O(3)-rich compositions ([Formula: see text]), cloudy materials were produced which contain inclusions of crystalline yttrium aluminium garnet (YAG) of diameter up to 40 µm in a glassy matrix. For Y(2)O(3)-poor compositions around x = 0.24, cloudy materials were also produced, but it was not possible to deduce whether this resulted from (i) sub-micron inclusions of a nano-crystalline or glassy material in a glassy matrix or (ii) a glass formed by spinodal decomposition. For x = 0.21, however, the sample cloudiness results from crystallization into at least two phases comprising yttrium aluminium perovskite and alumina. The associated pyrometric cooling curve shows slow recalescence events with a continuous and slow evolution of excess heat which contrasts with the sharp recalescence events observed for the crystallization of YAG at compositions near x = 0.375. The materials that are the most likely candidates for demonstrating homogeneous nucleation of a second liquid phase occur around x = 0.25, which corresponds to the limit for formation of a continuous random network of corner-shared AlO(4) tetrahedra.

Structure of glassy GeO2.

The full set of partial structure factors for glassy germania, or GeO2, were accurately measured by using the method of isotopic substitution in neutron diffraction in order to elucidate the nature of the pair correlations for this archetypal strong glass former. The results show that the basic tetrahedral Ge(O1/2)4 building blocks share corners with a mean inter-tetrahedral Ge-Ô-Ge bond angle of 132(2)°. The topological and chemical ordering in the resultant network displays two characteristic length scales at distances greater than the nearest neighbour. One of these describes the intermediate range order, and manifests itself by the appearance of a first sharp diffraction peak in the measured diffraction patterns at a scattering vector kFSDP≈1.53 Å-1, while the other describes so-called extended range order, and is associated with the principal peak at kPP = 2.66(1) Å-1. We find that there is an interplay between the relative importance of the ordering on these length scales for tetrahedral network forming glasses that is dominated by the extended range ordering with increasing glass fragility. The measured partial structure factors for glassy GeO2 are used to reproduce the total structure factor measured by using high energy x-ray diffraction and the experimental results are also compared to those obtained by using classical and first principles molecular dynamics simulations.

Glass fragility and atomic ordering on the intermediate and extended range.

The relation between the fragility of glass-forming systems, a parameter which describes many of their key physical characteristics, and atomic scale structure is investigated by using neutron diffraction to measure the topological and chemical ordering for germania, or GeO(2), which is an archetypal strong glass former. We find that the ordering for this and other tetrahedral network-forming glasses at distances greater than the nearest neighbor can be rationalized in terms of an interplay between the relative importance of two length scales. One of these is associated with an intermediate range, the other with an extended range and, with increasing glass fragility, it is the extended range ordering which dominates.