Chemomechanics of ionically conductive ceramics for electrical energy conversion and storage

Functional materials for energy conversion and storage exhibit strong coupling between electrochemistry and mechanics. For example, ceramics developed as electrodes for both solid oxide fuel cells and batteries exhibit cyclic volumetric expansion upon reversible ion transport. Such chemomechanical coupling is typically far from thermodynamic equilibrium, and thus is challenging to quantify experimentally and computationally. In situ measurements and atomistic simulations are under rapid development to explore how this coupling can be used to potentially improve both device performance and durability. Here, we review the commonalities of coupling between electrochemical and mechanical states in fuel cell and battery materials, illustrating with specific cases the progress in materials processing, in situ characterization, and computational modeling and simulation. We also highlight outstanding questions and opportunities in these applications – both to better understand the limiting mechanisms within the materials and to significantly advance the durability and predictability of device performance required for renewable energy conversion and storage.United States. Dept. of Energy (Basic Energy Sciences Division of Materials Sciences and Engineering, grant DE-SC0002633)United States. Dept. of Energy (Office of Science, Graduate Fellowship Program (DOE SCGF))United States. American Recovery and Reinvestment Act of 2009 (ORISE-ORAU, contract no. DE-AC05-06OR23100))United States. Dept. of Energy. Division of Materials Sciences and Engineering (MIT/DMSE Salapatas Fellowship)United States. Air Force Office of Scientific Research (Presidential Early Career Award in Science and Engineering (PECASE)

Norian ammonoids from the nayband formation (Iran) and their bearing on late triassic sedimentary and geodynamic history of the Iran plate

A Middle Norian (Alaunian 2) ammonoid assemblage from north of Esfahan (Central Iran) is described and chronostratigraphically evaluated. Formerly known as Distichites fauna, it represents a geographically widely distributed and stratigraphically important fossil level in the lower part of the Upper Triassic Nayband Formation. The new distichitid ammonoid genus Mesodistichites with the new species M. evolutus are introduced; additional faunal members are Noridiscites nodosus n. sp. and the leiostracean Stenarcestes diogenis and Pinacoceras cf. imperator. The Nayband Formation of the Esfahan region, belonging to the Zefreh-Soh Facies, is lithostratigraphically emended to contain three formally introduced members (Parsefid, Venher and Niazmargh members), which are all of Norian age, whereas Rhaetian sediments are missing. These members are correlated with Norian lithostratigraphic units of the type sequence of the formation in Nayband, eastern Iran. Integration of all Iranian Nayband data allows the recognition of three 3rd order sequences within this formation and the proof of a major pre- or syn-Jurassic unconformity across Central Iran and the Central-East Iranian Microcontinent (CEIM) related to the Main-Cimmerian event. Because of the latter and of major lithostratigraphic and facial differences, we propose to exclude the Nayband Formation from the Shemshak Group. A careful review of the available biostratigraphic data from northern and southern Iran let us further assume that the collision of the Iran Plate with Eurasia occurred in the later Early Carnian and was concurrent to the onset of the Carnian Humid Episode

Mechanical Strain Promotes Oligodendrocyte Differentiation by Global Changes of Gene Expression.

Differentiation of oligodendrocyte progenitor cells (OPC) to oligodendrocytes and subsequent axon myelination are critical steps in vertebrate central nervous system (CNS) development and regeneration. Growing evidence supports the significance of mechanical factors in oligodendrocyte biology. Here, we explore the effect of mechanical strains within physiological range on OPC proliferation and differentiation, and strain-associated changes in chromatin structure, epigenetics, and gene expression. Sustained tensile strain of 10-15% inhibited OPC proliferation and promoted differentiation into oligodendrocytes. This response to strain required specific interactions of OPCs with extracellular matrix ligands. Applied strain induced changes in nuclear shape, chromatin organization, and resulted in enhanced histone deacetylation, consistent with increased oligodendrocyte differentiation. This response was concurrent with increased mRNA levels of the epigenetic modifier histone deacetylase Hdac11. Inhibition of HDAC proteins eliminated the strain-mediated increase of OPC differentiation, demonstrating a role of HDACs in mechanotransduction of strain to chromatin. RNA sequencing revealed global changes in gene expression associated with strain. Specifically, expression of multiple genes associated with oligodendrocyte differentiation and axon-oligodendrocyte interactions was increased, including cell surface ligands (Ncam, ephrins), cyto- and nucleo-skeleton genes (Fyn, actinins, myosin, nesprin, Sun1), transcription factors (Sox10, Zfp191, Nkx2.2), and myelin genes (Cnp, Plp, Mag). These findings show how mechanical strain can be transmitted to the nucleus to promote oligodendrocyte differentiation, and identify the global landscape of signaling pathways involved in mechanotransduction. These data provide a source of potential new therapeutic avenues to enhance OPC differentiation in vivo.We gratefully acknowledge funding from the National Multiple Sclerosis Society (RG4855A1/1), the Human Frontiers Science Program (RGP0015/2009-C), and the National Research Foundation of Singapore through the Singapore-MIT Alliance for Research and Technology (SMART), BioSystems and Micromechanics (BioSyM) interdisciplinary research group

First record of Rhabdoceras suessi (Ammonoidea, Late Triassic) from the Transylvanian Triassic Series of the Eastern Carpathians (Romania) and a review of its biochronology, paleobiogeography and paleoecology

Abstract The occurrence of the heteromorphic ammonoid Rhabdoceras suessi Hauer, 1860, is recorded for the first time in the Upper Triassic limestone of the Timon-Ciungi olistolith in the Rarău Syncline, Eastern Carpathians. A single specimen of Rhabdoceras suessi co-occurs with Monotis (Monotis) salinaria that constrains its occurrence here to the Upper Norian (Sevatian 1). It is the only known heteromorphic ammonoid in the Upper Triassic of the Romanian Carpathians. Rhabdoceras suessi is a cosmopolitan species widely recorded in low and mid-paleolatitude faunas. It ranges from the Late Norian to the Rhaetian and is suitable for high-resolution worldwide correlations only when it co-occurs with shorter-ranging choristoceratids, monotid bivalves, or the hydrozoan Heterastridium. Formerly considered as the index fossil for the Upper Norian (Sevatian) Suessi Zone, by the latest 1970s this species lost its key biochronologic status among Late Triassic ammonoids, and it generated a controversy in the 1980s concerning the status of the Rhaetian stage. New stratigraphic data from North America and Europe in the subsequent decades resulted in a revised ammonoid biostratigraphy for the uppermost Triassic, the Rhaetian being reinstalled as the topmost stage in the current standard timescale of the Triassic. The geographic distribution of Rhabdoceras is compiled from published worldwide records, and its paleobiogeography and paleoecology are discussed

Combinatorial molecular optimization of cement hydrates

Despite its ubiquitous presence in the built environment, concrete’s molecular-level properties are only recently being explored using experimental and simulation studies. Increasing societal concerns about concrete’s environmental footprint have provided strong motivation to develop new concrete with greater specific stiffness or strength (for structures with less material). Herein, a combinatorial approach is described to optimize properties of cement hydrates. The method entails screening a computationally generated database of atomic structures of calcium-silicate-hydrate, the binding phase of concrete, against a set of three defect attributes: calcium-to-silicon ratio as compositional index and two correlation distances describing medium-range silicon-oxygen and calcium-oxygen environments. Although structural and mechanical properties correlate well with calcium-to-silicon ratio, the cross-correlation between all three defect attributes reveals an indentation modulus-to-hardness ratio extremum, analogous to identifying optimum network connectivity in glass rheology. We also comment on implications of the present findings for a novel route to optimize the nanoscale mechanical properties of cement hydrate.National Ready Mixed Concrete Association (Research sponsorship)Education Foundation (N.J.) (Research sponsorship)Portland Cement Association (Research sponsorship

Pericyte actomyosin-mediated contraction at the cell-material interface can modulate the microvascular niche

Pericytes physically surround the capillary endothelium, contacting and communicating with associated vascular endothelial cells via cell–cell and cell–matrix contacts. Pericyte–endothelial cell interactions thus have the potential to modulate growth and function of the microvasculature. Here we employ the experimental finding that pericytes can buckle a freestanding, underlying membrane via actin-mediated contraction. Pericytes were cultured on deformable silicone substrata, and pericyte-generated wrinkles were imaged via both optical and atomic force microscopy (AFM). The local stiffness of subcellular domains both near and far from these wrinkles was investigated by using AFM-enabled nanoindentation to quantify effective elastic moduli. Substratum buckling contraction was quantified by the normalized change in length of initially flat regions of the substrata (corresponding to wrinkle contour lengths), and a model was used to relate local strain energies to pericyte contractile forces. The nature of pericyte-generated wrinkling and contractile protein-generated force transduction was further explored by the addition of pharmacological cytoskeletal inhibitors that affected contractile forces and the effective elastic moduli of pericyte domains. Actin-mediated forces are sufficient for pericytes to exert an average buckling contraction of 38% on the elastomeric substrata employed in these in vitro studies. Actomyosin-mediated contractile forces also act in vivo on the compliant environment of the microvasculature, including the basement membrane and other cells. Pericyte-generated substratum deformation can thus serve as a direct mechanical stimulus to adjacent vascular endothelial cells, and potentially alter the effective mechanical stiffness of nonlinear elastic extracellular matrices, to modulate pericyte–endothelial cell interactions that directly influence both physiologic and pathologic angiogenesis.National Science Foundation (U.S.) (CAREER Award)National Science Foundation (U.S.) (Chemical, Bioengineering, Environmental, and Transport Systems-0644846)National Institutes of Health (U.S.) (EY 19533)National Institutes of Health (U.S.) (EY 15125

Earliest Triassic microbialites in the South China Block and other areas; controls on their growth and distribution

Earliest Triassic microbialites (ETMs) and inorganic carbonate crystal fans formed after the end-Permian mass extinction (ca. 251.4 Ma) within the basal Triassic Hindeodus parvus conodont zone. ETMs are distinguished from rarer, and more regional, subsequent Triassic microbialites. Large differences in ETMs between northern and southern areas of the South China block suggest geographic provinces, and ETMs are most abundant throughout the equatorial Tethys Ocean with further geographic variation. ETMs occur in shallow-marine shelves in a superanoxic stratified ocean and form the only widespread Phanerozoic microbialites with structures similar to those of the Cambro-Ordovician, and briefly after the latest Ordovician, Late Silurian and Late Devonian extinctions. ETMs disappeared long before the mid-Triassic biotic recovery, but it is not clear why, if they are interpreted as disaster taxa. In general, ETM occurrence suggests that microbially mediated calcification occurred where upwelled carbonate-rich anoxic waters mixed with warm aerated surface waters, forming regional dysoxia, so that extreme carbonate supersaturation and dysoxic conditions were both required for their growth. Long-term oceanic and atmospheric changes may have contributed to a trigger for ETM formation. In equatorial western Pangea, the earliest microbialites are late Early Triassic, but it is possible that ETMs could exist in western Pangea, if well-preserved earliest Triassic facies are discovered in future work

Bio-chronostratigraphic calibration of the Upper Carnian-Lower Norian magnetostratigraphic scale at Pizzo Mondello (Sicani Mountains, Sicily).

Pizzo Mondello section is known since 15 years because of the continuous Late Triassic pelagic record of great significance for the establishment of an integrated chronostratigraphy of the Late Triassic (Gullo et al. 1996; Muttoni et al. 2001, 2004). During the last 4 years, Pizzo Mondello section has been studied in detail to provide a new and high resolution integrated bio-chronostratigraphy for the calibration of the magnetostratigraphy and chemostratigraphy proposed by Muttoni et al. (2001, 2004), and now it is one of the GSSP candidates for the definition of the base of the Norian. The lowest 143 m of the Cherty Limestone, straddling the C/N boundary have been studied in detail. The preliminary data of the ongoing research have been presented in all the meetings of the STS from Albuquerque 2007 and here we summarize the final results. The key correlation to the standard marine Triassic Scale is provided by the ammonoids. They are relatively rare, however the available collections document the Upper Carnian Discotropites plinii and Gonionotites italicus Subzones, from meter 15 to meter 80 from the base of the section. The following 15 meters are poor in ammonoids, while higher up the lower part of the Lower Norian Guembelites jandianus Zone is documented by Dimorphites cf. n. sp.1 of Krystyn, 1980. Conodonts are very abundant and have a great potential as practical tool for global correlations. The abundance of specimens at Pizzo Mondello gave the opportunity to point out clear relationships among the five most widespread Upper Camian/Lower Norian conodont genera (Paragondolella, Carnepigondolella, Metapolygnathus, Epigondolella and Norigondolella) and to identify trends of the generic turnovers (Mazza et al. 2010). The two biomarkers so far proposed as possible marker events for the GSSP were the FAD of E. quadrata (sample FNP88A) and the FAD of M. communisti (sample NA35). However, the FAD of E. quadrata occurs within the Gonionotites italicus Subzone, while the FAD of M. communisti is on its top. Halobiids are extremely common in the Cherty Limestone and they have also a great potential for large scale correlations. Nine species of Halobia have been recognized: Halobia carnica, H. lenticularis, H. simplex, H. superba, H. cf. rugosa, H. radiata, H. austriaca, H. styriaca and H. mediterranea. The best possible marker for the base of the Norian is the first occurrence of Halobia austriaca, that is recorded in the middle of the interval between the record of the Gonionotites italicus Subzone and the Guembelites jandianus Zone. Radiolarians were found in few samples but with high diversity assemblages. In the upper Gonionotites italicus Subzone to the Guembelites jandianus Zone there is an overlap of species previously considered Late Carnian with species usually regarded as Early Norian. About 4 m above the FAD of E. quadrata, in the Gonionotites italicus Subzone, the first assemblage with Capnuchosphaera deweveri Kozur & Mostler, Capnuchosphaera tricornis De Wever, Kahlerosphaera norica Kozur & Mock and Xiphothecaella longa Kozur & Mock, usually referred to Early Norian, occurs. These integrated bio-chronostratigraphic studies lead to identify some possible GSSP marker events especially on conodonts and halobiids, which occur in the upper part of magnetozone PM 4n, within PM 4r and in the lower part of PM 5n. Possibly the most suitable magnetostratigraphic event to recognize the basal Norian is the base of magnetozone PM 5n, as already suggested by Krystyn et al. 2002 and Muttoni et al. 2004