Ferroic multipolar order and disorder in cyanoelpasolite molecular perovskites.

We use a combination of variable-temperature high-resolution synchrotron X-ray powder diffraction measurements and Monte Carlo simulations to characterize the evolution of two different types of ferroic multipolar order in a series of cyanoelpasolite molecular perovskites. We show that ferroquadrupolar order in [C3N2H5]2Rb[Co(CN)6] is a first-order process that is well described by a four-state Potts model on the simple cubic lattice. Likewise, ferrooctupolar order in [NMe4]2B[Co(CN)6] (B = K, Rb, Cs) also emerges via a first-order transition that now corresponds to a six-state Potts model. Hence, for these particular cases, the dominant symmetry breaking mechanisms are well understood in terms of simple statistical mechanical models. By varying composition, we find that the effective coupling between multipolar degrees of freedom-and hence the temperature at which ferromultipolar order emerges-can be tuned in a chemically sensible manner. This article is part of the theme issue 'Mineralomimesis: natural and synthetic frameworks in science and technology'.

Emergence of Long-Range Order in BaTiO_{3} from Local Symmetry-Breaking Distortions.

By using a symmetry motivated basis to evaluate local distortions against pair distribution function data, we show without prior bias, that the off-center Ti displacements in the archetypal ferroelectric BaTiO_{3} are zone centered and rhombohedral-like across its known ferroelectric and paraelectric phases. We construct a simple Monte Carlo model that captures our main experimental findings and demonstrate how the rich crystallographic phase diagram of BaTiO_{3} emerges from correlations of local symmetry-breaking distortions alone. Our results strongly support the order-disorder picture for these phase transitions, but can also be reconciled with the soft-mode theory of BaTiO_{3} that is supported by some spectroscopic techniques.

Adaptive response of a metal-organic framework through reversible disorder-disorder transitions.

The ultrahigh porosity and varied functionalities of porous metal-organic frameworks make them excellent candidates for applications that range widely from gas storage and separation to catalysis and sensing. An interesting feature of some frameworks is the ability to open their pores to a specific guest, enabling highly selective separation. A prerequisite for this is bistability of the host structure, which enables the framework to breathe, that is, to switch between two stability minima in response to its environment. Here we describe a porous framework DUT-8(Ni)-which consists of nickel paddle wheel clusters and carboxylate linkers-that adopts a configurationally degenerate family of disordered states in the presence of specific guests. This disorder originates from the nonlinear linkers arranging the clusters in closed loops of different local symmetries that in turn propagate as complex tilings. Solvent exchange stimulates the formation of distinct disordered frameworks, as demonstrated by high-resolution transmission electron microscopy and diffraction techniques. Guest exchange was shown to stimulate repeatable switching transitions between distinct disorder states.

Real-space refinement of single-crystal electron diffuse scattering and its application to Bi(2)Ru(2)O(7-δ).

A real-space atomistic refinement approach to the analysis of experimental electron diffraction patterns is described. The method employs the reverse Monte Carlo algorithm to produce atomistic configurations capable of qualitatively reproducing diffuse electron scattering patterns. Its implementation in the program EDRMC is described in detail, together with a number of additional constraints/restraints that can be used to guide the refinement process. In particular, appropriate restraints ensure the individual atomic displacements introduced to model the diffuse scattering patterns are simultaneously consistent with the known average structure. The approach is then used to interpret electron diffraction patterns measured for Bi(2)Ru(2)O(7-δ). The diffuse scattering patterns observed are shown to arise primarily from concerted translations of Bi atoms. These translations can be interpreted in terms of rotations of [O(')Bi(4) ] tetrahedra correlated along the [Formula: see text] crystal axes and uncorrelated along orthogonal directions.

Glass formation via structural fragmentation of a 2D coordination network.

The structure of a glass obtained by the melt quenching of a two-dimensional (2D) coordination network was examined. X-ray analyses disclosed a 2D-to-0D structural transformation before and after glass formation. The mechanism is unique to coordination compounds, as it is characterized by labile and flexible coordination bonds.

Changes in glucose, insulin, and growth hormone levels associated with bedrest.

Changes in plasma glucose, insulin, and growth hormone (HGH) resulting from exposure to 56 d of bedrest were determined in five healthy young male subjects. Blood samples were collected by repeated venous puncture at 4-h intervals for 48-h periods before bedrest, at 10, 20, 30, 42 and 54 d after confinement to bed and at 10 and 20 d after bedrest. Changes in the daily levels of these factors for each subject were expressed as the mean of the six samples per 24-h period. The level of HGH dropped after 10 d of bedrest, then showed a 1.5-fold increase at 20 d (p less than 0.05) and subsequently decreased gradually reaching levels of 2.5 mg/ml/24 h, well below pre-bedrest controls of 4.2 mg/ml/24 h, by the 54th d. In spite of a marked increase in the daily plasma insulin levels during the first 30 d of bedrest, glucose levels remained unchanged. Beyond 30 d of bedrest, insulin began decreasing toward pre-bedrest levels and glucose followed with a similar reduction to below the control levels of 75 mg/100 ml/24 h on day 54. The daily mean changes reflect a change in the amplitude of the diurnal variation. The daily peak in plasma insulin shifted progressively to the late evening during the bedrest period.

Flexibility of zeolitic imidazolate framework structures studied by neutron total scattering and the reverse Monte Carlo method.

The zeolitic imidazolate framework ZIF-4 undergoes an amorphization transition at about 600 K, and then transforms at about 700 K to ZIF-zni, the densest of the crystalline ZIFs. This series of long-range structural rearrangements must give a corresponding series of changes in the local structure, but these have not previously been directly investigated. Through analysis of neutron total diffraction data by reverse Monte Carlo modelling, we assess the changes in flexibility across this series, identifying the key modes of flexibility within ZIF-4 and the amorphous phase. We show that the ZnN4 tetrahedra remain relatively rigid, albeit less so than SiO4 tetrahedra in silicates. However, the extra degrees of freedom afforded by the imidazolate ligand, compared to silicate networks, vary substantially between phases, with a twisting motion out of the plane of the ligand being particularly important in the amorphous phase. Our results further demonstrate the feasibility of reverse Monte Carlo simulations for studying intermolecular interactions in solids, even in cases, such as the ZIFs, where the pair distribution function is dominated by intramolecular peaks.

eScience for molecular-scale simulations and the eMinerals project.

We review the work carried out within the eMinerals project to develop eScience solutions that facilitate a new generation of molecular-scale simulation work. Technological developments include integration of compute and data systems, developing of collaborative frameworks and new researcher-friendly tools for grid job submission, XML data representation, information delivery, metadata harvesting and metadata management. A number of diverse science applications will illustrate how these tools are being used for large parameter-sweep studies, an emerging type of study for which the integration of computing, data and collaboration is essential.

Advances in the treatment of patients with pancreatic cancer: improvement in symptoms and survival time. The San Antonio Drug Development Team.

Pancreatic cancer is a major cause of death from cancer in both men and women in the USA and Europe. The disease causes pain and has a significant impact on the performance status of the patient. In a randomized trial vs 5-fluorouracil, the novel nucleoside analogue gemcitabine (GEMZAR) has been shown to provide clinical benefit for patients (decreased pain and improved performance status) as well as to improve the time to tumour progression and survival for patients with the disease. There are also other new agents that are presented in this discussion, such as the multi-targeted antifolate MTA, capecitabine and the ONYX-015 adenovirus, which replicates in, and kills, only p53-abnormal cells, which have the potential to have an impact on this terrible disease.