Incorporation of tetrahedral ferric iron in hydrous ringwoodite

Hydrous Fo_{91} ringwoodite crystals were synthesized at 20 GPa and high-temperature conditions using a multi-anvil press. Recovered crystals were analyzed using electron microprobe analysis, Raman spectroscopy, infrared spectroscopy, synchrotron Mössbauer spectroscopy, single-crystal X-ray diffraction, and single-crystal Laue neutron diffraction, to carefully characterize the chemistry and crystallography of the samples. Analysis of the combined data sets provides evidence for the presence of tetrahedrally coordinated ferric iron and multiple hydrogen incorporation mechanisms within these blue-colored iron-bearing ringwoodite crystals. Tetrahedral ferric iron is coupled with cation disorder of silicon onto the octahedrally coordinated site. Cation disorder in mantle ringwoodite minerals may be promoted in the presence of water, which could have implications for current models of seismic velocities within the transition zone. Additionally, the presence of tetrahedrally coordinated ferric iron may cause the blue color of many ringwoodite and other high-pressure crystals

Dolomite-IV : Candidate structure for a carbonate in the Earth's lower mantle

We report the crystal structure of dolomite-IV, a high-pressure polymorph of Fe-dolomite stabilized at 115 GPa and 2500 K. It is orthorhombic, space group Pnma, a =10.091(3), b = 8.090(7), c = 4.533(3) Å, V = 370.1(4) Å3 at 115.2 GPa and ambient temperature. The structure is based on the presence of threefold C3O9 carbonate rings, with carbon in tetrahedral coordination. The starting Fe-dolomite single crystal during compression up to 115 GPa transforms into dolomite-II (at 17 GPa) and dolomite-IIIb (at 36 GPa). The dolomite-IIIb, observed in this study, is rhombohedral, space group R3, a =11.956(3), c =13.626(5) Å, V =1686.9(5) Å3 at 39.4 GPa. It is different from a previously determined dolomite-III structure, but topologically similar. The density increase from dolomite-IIIb to dolomite IV is ca. 3%. The structure of dolomite-IV has not been predicted, but it presents similarities with the structural models proposed for the high-pressure polymorphs of magnesite, MgCO3. A ring-carbonate structure match with spectroscopic analysis of high-pressure forms of magnesite-siderite reported in the literature, and, therefore, is a likely candidate structure for a carbonate at the bottom of the Earth's mantle, at least for magnesitic and dolomitic compositions

Dolomite-IV : Candidate structure for a carbonate in the Earth's lower mantle

We report the crystal structure of dolomite-IV, a high-pressure polymorph of Fe-dolomite stabilized at 115 GPa and 2500 K. It is orthorhombic, space group Pnma, a =10.091(3), b = 8.090(7), c = 4.533(3) \uc5, V = 370.1(4) \uc53 at 115.2 GPa and ambient temperature. The structure is based on the presence of threefold C3O9 carbonate rings, with carbon in tetrahedral coordination. The starting Fe-dolomite single crystal during compression up to 115 GPa transforms into dolomite-II (at 17 GPa) and dolomite-IIIb (at 36 GPa). The dolomite-IIIb, observed in this study, is rhombohedral, space group R3, a =11.956(3), c =13.626(5) \uc5, V =1686.9(5) \uc53 at 39.4 GPa. It is different from a previously determined dolomite-III structure, but topologically similar. The density increase from dolomite-IIIb to dolomite IV is ca. 3%. The structure of dolomite-IV has not been predicted, but it presents similarities with the structural models proposed for the high-pressure polymorphs of magnesite, MgCO3. A ring-carbonate structure match with spectroscopic analysis of high-pressure forms of magnesite-siderite reported in the literature, and, therefore, is a likely candidate structure for a carbonate at the bottom of the Earth's mantle, at least for magnesitic and dolomitic compositions

Relatively oxidized conditions for diamond formation at Udachnaya (Siberia)

Thanks to the physical strength of diamonds and their relatively unreactive chemical nature, their mineral inclusions may remain exceptionally preserved from alteration processes and chemical exchanges with surrounding minerals, fluids and/or melts following diamond formation. Cr-bearing spinels are relatively common inclusions found in peridotitic diamonds and important oxybarometers providing information about the oxygen fugacity (fO2) of their source mantle rocks. Here, we investigated a magnesiochromite-olivine touching pair in a diamond from the Udachnaya kimberlite (Siberia) by in situ single-crystal X-ray diffraction and energy-domain synchrotron Mossbauer spectroscopy, aiming to constrain the physical-chemical conditions of diamond formation and to explore the redox state of this portion of the Siberian craton when the diamond was formed. The P-T-fO(2) entrapment conditions of the inclusion pair, determined by thermo- and oxybarometric analyses, are similar to 5.7(0.4) GPa and similar to 1015(50) ? (although entrapment at higher T and re-equilibration during subsequent mantle storage are also possible) and fO(2) near the enstatite-magnesite-olivine-diamond (EMOD) buffer. The determined fO(2) is similar to, or slightly more oxidized than, those of xenoliths from Udachnaya, but whilst the xenoliths last equilibrated with the surrounding mantle just prior to their entrainment in the kimberlite at similar to 360 Ma, the last equilibration of the inclusion pair is much older, occurring at 3.5-3.1, similar to 2 or similar to 1.8 Ga before final encapsulation in its host diamond. Hence, the similarity between xenoliths and inclusion fO(2) values indicates that the modern redox state of this portion of the Siberian lithosphere was likely attained relatively early after its formation and may have persisted for billions of years after diamond formation, at least at the local scale. Moreover, the oxygen fugacity determination for the inclusion pair provides direct evidence of diamond formation near the EMOD buffer and is consistent with recent models suggesting relatively oxidized, water-rich CHO fluids as the most likely parents for lithospheric diamonds

Antibiotic treatment-induced dysbiosis differently affects BDNF and TrkB expression in the brain and in the gut of juvenile mice

Antibiotic use during adolescence may result in dysbiosis-induced neuronal vulnerability both in the enteric nervous system (ENS) and central nervous system (CNS) contributing to the onset of chronic gastrointestinal disorders, such as irritable bowel syndrome (IBS), showing significant psychiatric comorbidity. Intestinal microbiota alterations during adolescence influence the expression of molecular factors involved in neuronal development in both the ENS and CNS. In this study, we have evaluated the expression of brain-derived neurotrophic factor (BDNF) and its high-affinity receptor tropomyosin-related kinase B (TrkB) in juvenile mice ENS and CNS, after a 2-week antibiotic (ABX) treatment. In both mucosa and mucosa-deprived whole-wall small intestine segments of ABX-treated animals, BDNF and TrKB mRNA and protein levels significantly increased. In longitudinal muscle-myenteric plexus preparations of ABX-treated mice the percentage of myenteric neurons staining for BDNF and TrkB was significantly higher than in controls. After ABX treatment, a consistent population of BDNF-and TrkB-immunoreactive neurons costained with SP and CGRP, suggesting up-regulation of BDNF signaling in both motor and sensory myenteric neurons. BDNF and TrkB protein levels were downregulated in the hippocampus and remained unchanged in the prefrontal cortex of ABX-treated animals. Immunostaining for BDNF and TrkB decreased in the hippocampus CA3 and dentate gyrus subregions, respectively, and remained unchanged in the prefrontal cortex. These data suggest that dysbiosis differentially influences the expression of BDNF-TrkB in the juvenile mice ENS and CNS. Such changes may potentially contribute later to the development of functional gut disorders, such as IBS, showing psychiatric comorbidity

Beltrandoite, a new root-name in the högbomite supergroup: the Mg end-member magnesiobeltrandoite-2N3S

Magnesiobeltrandoite-2N3S, ideally Mg6Al20Fe3+2 O38(OH)2, is a new member of the h\uf6gbomite supergroup of minerals. It occurs in magnesian chloritites of a metamorphosed layered mafic complex in the Etirol-Levaz continental slice, middle Valtournenche, Aosta Valley, Italy. Magnesiobeltrandoite-2N3S grows in a fine-grained chlorite matrix associated as inclusions to relict pre-Alpine hercynite spinels and dolomite in cm- to dm-long darker boudins, which are cut by corundum\ufeclinochlore \ub1 dolomite veins. It occurs as subhedral to euhedral black crystals ( 3c50\u2013400mm), dark reddish-brown in thin section. It shows dark brown streak and vitreous lustre. It is brittle, with no cleavage observed and uneven fracture. Mohs hardness 486\u20136\ubd. Dcalc = 3.93 g \ub7 cm3. It shows no fluorescence under UV radiation and no cathodoluminescence. The mineral is optically uniaxial (\u2013) with an estimated mean refractive index of ca. 1.80. Pleochroism is weak with e = deep reddish brown (along c axis) and v = reddish brown ( a5 c). Absorption is E > O. The Raman spectrum shows a weak and strongly polarized broad OH-characteristic absorption centred at 3364 cm1. Electron microprobe analysis combined with Synchrotron M\uf6ssbauer source spectrometry yielded the following empirical formula based on 40 anions per formula unit (pfu) [Al18.36Mg3.96Fe2+2:52Fe3+2:08Ti0.56Cr0.40Zn0.06V3+0.03Mn0.02]S28O38(OH)2. The ideal formula is Mg6Al20Fe3+2O38(OH)2.The eight strongest lines in the X-ray powder diffraction pattern are [dobs/A (I) (h k l)]: 2.858 (42) (1 1 0), 2.735 (51) (1 0 7), 2.484 (46) (0 1 8), 2.427 (100) (1 1 5), 1.568 (29) (1 2 8), 1.514 (30) (0 2 12), 1.438 (42) (2 0 13), and 1.429 (72) (2 2 0). The crystal structure of magnesiobeltrandoite-2N3S [P3m1, a = 5.7226(3), c = 23.0231(9)A, V = 652.95(5)A 3] was refined from X-ray single-crystal data to R1 = 0.022; it is isostructural with magnesioh\uf6gbomite-2N3S

The yeast P5 type ATPase, Spf1, regulates manganese transport into the endoplasmic reticulum

The endoplasmic reticulum (ER) is a large, multifunctional and essential organelle. Despite intense research, the function of more than a third of ER proteins remains unknown even in the well-studied model organism Saccharomyces cerevisiae. One such protein is Spf1, which is a highly conserved, ER localized, putative P-type ATPase. Deletion of SPF1 causes a wide variety of phenotypes including severe ER stress suggesting that this protein is essential for the normal function of the ER. The closest homologue of Spf1 is the vacuolar P-type ATPase Ypk9 that influences Mn2+ homeostasis. However in vitro reconstitution assays with Spf1 have not yielded insight into its transport specificity. Here we took an in vivo approach to detect the direct and indirect effects of deleting SPF1. We found a specific reduction in the luminal concentration of Mn2+ in ∆spf1 cells and an increase following it’s overexpression. In agreement with the observed loss of luminal Mn2+ we could observe concurrent reduction in many Mn2+-related process in the ER lumen. Conversely, cytosolic Mn2+-dependent processes were increased. Together, these data support a role for Spf1p in Mn2+ transport in the cell. We also demonstrate that the human sequence homologue, ATP13A1, is a functionally conserved orthologue. Since ATP13A1 is highly expressed in developing neuronal tissues and in the brain, this should help in the study of Mn2+-dependent neurological disorders

Ultra-fast yttrium hydride chemistry at high pressures via non-equilibrium states induced by x-ray free electron laser

Controlling the formation and stoichiometric content of desired phases of materials has become a central interest for the study of a variety of fields, notably high temperature superconductivity under extreme pressures. The further possibility of accessing metastable states by initiating reactions by x-ray triggered mechanisms over ultra-short timescales is enabled with the development of x-ray free electron lasers (XFEL). Utilizing the exceptionally high brilliance x-ray pulses from the EuXFEL, we report the synthesis of a previously unobserved yttrium hydride under high pressure, along with non-stoichiometric changes in hydrogen content as probed at a repetition rate of 4.5\,MHz using time-resolved x-ray diffraction. Exploiting non-equilibrium pathways we synthesize and characterize a hydride with yttrium cations in an \textit{A}15 structure type at 125\,GPa, predicted using crystal structure searches, with a hydrogen content between 4.0--5.75 hydrogens per cation, that is enthalpically metastable on the convex hull. We demonstrate a tailored approach to changing hydrogen content using changes in x-ray fluence that is not accessible using conventional synthesis methods, and reveals a new paradigm in metastable chemical physics

Supportive interventions to improve physiological and psychological health outcomes among patients undergoing cystectomy: A systematic review

Background Our understanding of effective perioperative supportive interventions for patients undergoing cystectomy procedures and how these may affect short and long-term health outcomes is limited. Methods Randomised controlled trials involving any non-surgical, perioperative interventions designed to support or improve the patient experience for patients undergoing cystectomy procedures were reviewed. Comparison groups included those exposed to usual clinical care or standard procedure. Studies were excluded if they involved surgical procedure only, involved bowel preparation only or involved an alternative therapy such as aromatherapy. Any short and long-term outcomes reflecting the patient experience or related urological health outcomes were considered. Results 19 articles (representing 15 individual studies) were included for review. Heterogeneity in interventions and outcomes across studies meant meta-analyses were not possible. Participants were all patients with bladder cancer and interventions were delivered over different stages of the perioperative period. The overall quality of evidence and reporting was low and outcomes were predominantly measured in the short-term. However, the findings show potential for exercise therapy, pharmaceuticals, ERAS protocols, psychological/educational programmes, chewing gum and nutrition to benefit a broad range of physiological and psychological health outcomes. Conclusions Supportive interventions to date have taken many different forms with a range of potentially meaningful physiological and psychological health outcomes for cystectomy patients. Questions remain as to what magnitude of short-term health improvements would lead to clinically relevant changes in the overall patient experience of surgery and long-term recovery