Revealing the Complex Nature of Bonding in the Binary High-Pressure Compound FeO_{2}.

Extreme pressures and temperatures are known to drastically affect the chemistry of iron oxides, resulting in numerous compounds forming homologous series nFeOmFe_{2}O_{3} and the appearance of FeO_{2}. Here, based on the results of in situ single-crystal x-ray diffraction, Mössbauer spectroscopy, x-ray absorption spectroscopy, and density-functional theory+dynamical mean-field theory calculations, we demonstrate that iron in high-pressure cubic FeO_{2} and isostructural FeO_{2}H_{0.5} is ferric (Fe^{3+}), and oxygen has a formal valence less than 2. Reduction of oxygen valence from 2, common for oxides, down to 1.5 can be explained by a formation of a localized hole at oxygen sites.

A human skin model to evaluate the protective effect of compounds against UVA damage.

OBJECTIVE: The main function of skin is to protect the body from external aggressions. Over time, normal skin ageing is accelerated by external stresses such as smoking, pollution, chemical products and radiation. UV light, in particular UVA, causes DNA damage, apoptosis and morphological modifications, which are responsible for both premature ageing and cancer. The aim of this study was to establish a discriminatory and sufficiently reproducible cutaneous model for evaluating UVA damage, to enable testing for effectiveness of potentially protective compounds. METHODS: The cutaneous model is based on Human skin explants irradiated with UVA. Deleterious effects on epidermis were observed and quantified by haematoxylin-eosin staining and by immunofluorescence of ɣ-H2Ax, cytokeratin 5, involucrin and loricrin protein. Dermis deterioration was evaluated by transmission electronic microscopy and zymography in situ. RESULTS: We were able to observe and quantify deleterious effects associated with UVA irradiation: epidermal and dermal disruption, appearance of Sunburn cells, increased DNA damage and induced apoptosis. The use of this model in the evaluation of protective compounds was first confirmed using sunscreens, then further validated with a panel of active ingredients which showed beneficial effects on epidermis morphology and DNA integrity after UVA exposure. CONCLUSION: We have developed a model and a standardized protocol, based on the use of human skin explants, which allows us to explore the protective effect of active ingredients to environmental stresses such as UVA.

OBJECTIFS: La fonction principale de la peau est de protéger le corps des agressions externes. Au cours du temps, le vieillissement naturel de la peau est accéléré par des stress externes comme la cigarette, la pollution, les produits chimiques et les radiations solaires. Le rayonnement ultraviolet, en particulier les UVA, cause des dommages de l'ADN, l'apoptose et des modifications morphologiques qui sont responsables du vieillissement prématuré et de cancers. Le but de cette étude est d'établir un modèle cutané reproductible et discriminatoire pour évaluer les dommages créé par les UVA et tester l'efficacité de potentiels produits protecteurs. MÉTHODES: Ce modèle cutané est basé sur un explant de peau humaine irradié aux UVA. Les effets délétères sur l'épiderme sont observés et quantifiés par coloration Hématoxyline-éosine et par des immunofluorescence des protéines É£-H2Ax, cytokératine 5, involucrine et loricrine. Le détérioration du derme est évaluée par microscopie électronique à transmission et par zymographie in situ. RÉSULTATS: Nous avons observé et quantifié des effets délétères associés aux irradiation UVA: détérioration de l'épiderme et du derme, apparition de cellules "coup de soleil", augmentation des dommages de l'ADN et l'induction de l'apoptose. L'utilisation du modèle pour tester des nouveaux composés a été premièrement validée avec l'utilisation d'un filtre solaire puis validée par le test d'un panel d'ingrédients actifs qui ont montré des effets bénéfiques sur la morphologie de l'épiderme et l'intégrité de l'ADN après exposition aux UVA. CONCLUSION: Nous avons développé un modèle et un protocole standardisé basé sur l'utilisation d'un explant de peau humaine qui permet d'explorer l'effet protecteur ingrédients actifs contre des stress environnementaux comme les UVA.

3D imaging of cleared human skin biopsies using light-sheet microscopy: A new way to visualize in-depth skin structure.

BACKGROUND: Human skin is composed of the superimposition of tissue layers of various thicknesses and components. Histological staining of skin sections is the benchmark approach to analyse the organization and integrity of human skin biopsies; however, this approach does not allow 3D tissue visualization. Alternatively, confocal or two-photon microscopy is an effective approach to perform fluorescent-based 3D imaging. However, owing to light scattering, these methods display limited light penetration in depth. The objectives of this study were therefore to combine optical clearing and light-sheet fluorescence microscopy (LSFM) to perform in-depth optical sectioning of 5 mm-thick human skin biopsies and generate 3D images of entire human skin biopsies. MATERIALS AND METHODS: A benzyl alcohol and benzyl benzoate solution was used to successfully optically clear entire formalin fixed human skin biopsies, making them transparent. In-depth optical sectioning was performed with LSFM on the basis of tissue-autofluorescence observations. 3D image analysis of optical sections generated with LSFM was performed by using the Amira® software. RESULTS: This new approach allowed us to observe in situ the different layers and compartments of human skin, such as the stratum corneum, the dermis and epidermal appendages. With this approach, we easily performed 3D reconstruction to visualise an entire human skin biopsy. Finally, we demonstrated that this method is useful to visualise and quantify histological anomalies, such as epidermal hyperplasia. CONCLUSION: The combination of optical clearing and LSFM has new applications in dermatology and dermatological research by allowing 3D visualization and analysis of whole human skin biopsies.

Simple mechanical cues could explain adipose tissue morphology.

The mechanisms by which organs acquire their functional structure and realize its maintenance (or homeostasis) over time are still largely unknown. In this paper, we investigate this question on adipose tissue. Adipose tissue can represent 20 to 50% of the body weight. Its investigation is key to overcome a large array of metabolic disorders that heavily strike populations worldwide. Adipose tissue consists of lobular clusters of adipocytes surrounded by an organized collagen fiber network. By supplying substrates needed for adipogenesis, vasculature was believed to induce the regroupment of adipocytes near capillary extremities. This paper shows that the emergence of these structures could be explained by simple mechanical interactions between the adipocytes and the collagen fibers. Our assumption is that the fiber network resists the pressure induced by the growing adipocytes and forces them to regroup into clusters. Reciprocally, cell clusters force the fibers to merge into a well-organized network. We validate this hypothesis by means of a two-dimensional Individual Based Model (IBM) of interacting adipocytes and extra-cellular-matrix fiber elements. The model produces structures that compare quantitatively well to the experimental observations. Our model seems to indicate that cell clusters could spontaneously emerge as a result of simple mechanical interactions between cells and fibers and surprisingly, vasculature is not directly needed for these structures to emerge.

Pressure-induced penetration of guest molecules in high-silica zeolites: the case of mordenite.

A synthetic high-silica mordenite (HS-MOR) has been compressed in both non-penetrating (silicone oil, s.o.) and penetrating [methanol : ethanol : water (16 : 3 : 1) (m.e.w.), water : ethanol (3 : 1) (w.e.), and ethylene glycol (e.gl.)] pressure transmitting media (PTM). In situ high-pressure (HP) synchrotron X-ray powder diffraction (XRPD) experiments allowed the unit cell parameters to be followed up to 1.6, 1.8, 8.4, and 6.7 GPa in s.o., w.e., m.e.w., and e.gl., respectively. Moreover, e.gl. was also used as a PTM in in situ HP Raman and ex situ IR experiments. The structural refinement of HS-MOR compressed in e.gl. at 0.1 GPa - the lowest investigated pressure - revealed the presence of 3.5 ethylene glycol molecules per unit cell. The infrared spectrum of the recovered sample, after compression to 1 GPa, is consistent with the insertion of ethylene glycol molecules in the pores. XRPD and Raman spectroscopy experiments performed under pressure indicated the insertion of a small number of guest molecules. Ethylene glycol is partially retained inside mordenite upon pressure release. A symmetry lowering was observed in s.o. above 0.8 GPa, while above 1.6 GPa the patterns indicated a rapid loss of long range order. From ambient pressure (Pamb) to 1.6 GPa, a high cell volume contraction (ΔV = -9.5%) was determined. The patterns collected with penetrating PTM suggested the penetration of guest molecules into the porous host matrix, starting from a very low P regime. The entrapment of PTM molecules inside micropores contributes to the stiffening of the structure and, as a consequence, to the decrease of the compressibility with respect to that measured in s.o. From the structural point of view, HS-MOR reacts to compression and to the penetration of different guest species with appropriate framework deformations. Interestingly, ethylene glycol is partially retained inside mordenite upon pressure release, which is of importance for potential application of this composite material.

Role of zinc and niobium in the giant piezoelectric response of PbZn(1/3)Nb(2/3)O(3).

Relaxor ferroelectric perovskites are highly polarizable and can exhibit giant coupling between elastic strain and an applied electric field. Here, we report an in situ extended X-ray absorption fine structure (EXAFS) study of a PbZn1/3Nb2/3O3 (PZN) single crystal as a function of the electric field. We show that the strong dipoles in the NbO6 octahedra bonds are aligned along the four ⟨011⟩ directions close to the orientation of the electric field, while a small reversible polar shift occurs for Zn in the direction of the electric field, i.e., positive or negative. This reversible Zn-O polar shift is proposed to play an important role in both the "easy" switching of the ferroelectric polarization and the giant piezoelectric effect in PZN.

Oxygen storage capacity and structural flexibility of LuFe2O4+x (0≤x≤0.5).

Combining functionalities in devices with high performances is a great challenge that rests on the discovery and optimization of materials. In this framework, layered oxides are attractive for numerous purposes, from energy conversion and storage to magnetic and electric properties. We demonstrate here the oxygen storage ability of ferroelectric LuFe2O4+x within a large x range (from 0 to 0.5) and its cycling possibility. The combination of thermogravimetric analyses, X-ray diffraction and transmission electron microscopy evidences a complex oxygen intercalation/de-intercalation process with several intermediate metastable states. This topotactic mechanism is mainly governed by nanoscale structures involving a shift of the cationic layers. The ferrite is highly promising because absorption begins at a low temperature (~=200 °C), occurs in a low oxygen pressure and the uptake of oxygen is reversible without altering the quality of the crystals. The storage/release of oxygen coupled to the transport and magnetic properties of LnFe2O4 opens the door to new tunable multifunctional applications.

Integrated modelling for Sustainability Appraisal of urban river corridors: going beyond compartmentalised thinking.

Sustainability Appraisal (SA) is a complex task that involves integration of social, environmental and economic considerations and often requires trade-offs between multiple stakeholders that may not easily be brought to consensus. Classical SA, often compartmentalised in the rigid boundary of disciplines, can facilitate discussion, but can only partially inform decision makers as many important aspects of sustainability remain abstract and not interlinked. A fully integrated model can overcome compartmentality in the assessment process and provides opportunity for a better integrative exploratory planning process. The objective of this paper is to explore the benefit of an integrated modelling approach to SA and how a structured integrated model can be used to provide a coherent, consistent and deliberative platform to assess policy or planning proposals. The paper discusses a participative and integrative modelling approach to urban river corridor development, incorporating the principal of sustainability. The paper uses a case study site in Sheffield, UK, with three alternative development scenarios, incorporating a number of possible riverside design features. An integrated SA model is used to develop better design by optimising different design elements and delivering a more sustainable (re)-development plan. We conclude that participatory integrated modelling has strong potential for supporting the SA processes. A high degree of integration provides the opportunity for more inclusive and informed decision-making regarding issues of urban development. It also provides the opportunity to reflect on their long-term dynamics, and to gain insights on the interrelationships underlying persistent sustainability problems. Thus the ability to address economic, social and environmental interdependencies within policies, plans, and legislations is enhanced.

Structural description of the macroscopic piezo- and ferroelectric properties of lead zirconate titanate.

An in situ structural description of the origin of the ferroelectric properties as a function of the applied electric field E was obtained by synchrotron x-ray diffraction. A setup was used to average the effects of the preferred orientation induced by the strong piezoelectric strain and solve in situ the crystal structure as a function of the applied electric field. Hence, we were able to describe the microscopic origin of the macroscopic ferro- and piezoelectric properties of the most widely used ferroelectric material, lead zirconate titanate.

Soft mode doublet in PbMg{1/3}Nb{2/3}O{3} relaxor investigated with hyper-Raman scattering.

Hyper-Raman scattering experiments suggest that a splitting of the lowest F{1u}-symmetry mode of PbMg{1/3}Nb{2/3}O{3} crystal occurs in a wide temperature range around its Burns temperature T{d}≈630 K. The upper-frequency component, earlier investigated by inelastic neutron scattering experiments above T{d}, appears to be underdamped even hundred of degrees below T{d}. The lower-frequency component, known below T{d} from far-IR spectroscopy, actually becomes underdamped above T{d}. This suggests that the lower-frequency mode is the "primary" polar soft mode of PbMg{1/3}Nb{2/3}O{3}, responsible for the Curie-Weiss behavior of its dielectric permittivity above T{d}.

Pressure-induced structural transition in LuFe2O4: towards a new charge ordered state.

The electronic ferroelectric lutetium ferrite (LuFe(2)O(4)) was studied by x-ray diffraction as a function of pressure. Pressure is shown to induce an irreversible rhombohedral to orthorhombic transition leading to a supercell determined by the combination of electron and synchrotron x-ray diffraction. This new configuration is proposed to be charge ordered in agreement with the results of resistivity measurements.

High-pressure structural and vibrational study of PbZr0.40Ti0.60O3.

The high-pressure structure and dynamics of PbZr0.40Ti0.60O3 were investigated by means of neutron diffraction, X-ray diffraction, and resonance Raman spectroscopy. The complex (P4mm, Cm, Cc, F1, F1) phase transition sequence is characterized by these techniques. On the basis of the results of structure refinements, the high-pressure behavior of the spontaneous polarization, the (Zr,Ti)O6 rotation angles, and the polarization rotation angle are obtained. Moreover, resonance Raman spectra combined with previous Raman data in the literature provide evidence that the pressure-induced transition to the monoclinic Cm space group and the above transition sequence terminating in a paraelectric state are general features of Pb(Zr(1-x)Ti(x))O3 (0.48 < or = x < or = 1).

High-pressure studies of (Mg0.9Fe0.1)2SiO4 olivine using raman spectroscopy, X-ray diffraction, and mössbauer spectroscopy.

High-pressure studies of (Mg(0.9)Fe(0.1))2SiO4 olivine were performed at ambient temperature using X-ray diffraction, Raman spectroscopy, and Mössbauer spectroscopy. At approximately 40 GPa, a change of compressibility associated with saturation of the anisotropic compression mechanism was detected. This change is interpreted to result from the appearance of Si2O7 dimer defects, as deduced from Raman spectroscopy; the appearance of such defects also accounts for the previously reported pressure-induced amorphization observed for this material upon additional compression. Furthermore, this behavior is followed by a spin crossover of Fe(2+) that occurs over a wide pressure range, as revealed by Mössbauer spectroscopy.

Molecular and ecological evidence for small-scale isolation by distance in an endangered damselfly, Coenagrion mercuriale.

Coenagrion mercuriale (Charpentier) (Odonata: Zygoptera) is one of Europe's most threatened damselflies and is listed in the European Habitats directive. We combined an intensive mark-release-recapture (MRR) study with a microsatellite-based genetic analysis for C. mercuriale from the Itchen Valley, UK, as part of an effort to understand the dispersal characteristics of this protected species. MRR data indicate that adult damselflies are highly sedentary, with only a low frequency of interpatch movement that is predominantly to neighbouring sites. This restricted dispersal leads to significant genetic differentiation throughout most of the Itchen Valley, except between areas of continuous habitat, and isolation by distance (IBD), even though the core populations are separated by less than 10 km. An urban area separating some sites had a strong effect on the spatial genetic structure. Average pairwise relatedness between individual damselflies is positive at short distances, reflecting fine-scale genetic clustering and IBD both within- and between-habitat patches. Damselflies from a fragmented habitat have higher average kinship than those from a large continuous population, probably because of poorer dispersal and localized breeding in the former. Although indirect estimates of gene flow must be interpreted with caution, it is encouraging that our results indicate that the spatial pattern of genetic variation matches closely with that expected from direct observations of movement. These data are further discussed with respect to possible barriers to dispersal within the study site and the ecology and conservation of C. mercuriale. To our knowledge, this is the first report of fine-scale genetic structuring in any zygopteran species.