386 research outputs found

    Frictional Behaviour, Wear and Comminution of Synthetic Porous Geomaterials

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    During shearing in geological environments, frictional processes, including the wear of sliding rock surfaces, control the nature of the slip events. Multiple studies focusing on natural samples have investigated the frictional behaviour of a large suite of geological materials. However, due to the varied and heterogeneous nature of geomaterials, the individual controls of material properties on friction and wear remain unconstrained. Here, we use variably porous synthetic glass samples (8, 19 and 30% porosity) to explore the frictional behaviour and development of wear in geomaterials at low normal stresses ( 641\ua0MPa). We propose that porosity provides an inherent roughness to material which wear and abrasion cannot smooth, allowing material at the pore margins to interact with the slip surface. This results in an increase in measured friction coefficient from <0.4 for 8% porosity, to <0.55 for 19% porosity and 0.6\u20130.8 for 30% porosity for the slip rates evaluated. For a given porosity, wear rate reduces with slip rate due to less asperity interaction time. At higher slip rates, samples also exhibit slip weakening behaviour, either due to evolution of the slipping zone or by the activation of temperature-dependent microphysical processes. However, heating rate and peak temperature may be reduced by rapid wear rates as frictional heating and wear compete. The higher wear rates and reduced heating rates of porous rocks during slip may delay the onset of thermally triggered dynamic weakening mechanisms such as flash heating, frictional melting and thermal pressurisation. Hence porosity, and the resultant friction coefficient, work, heating rate and wear rate, of materials can influence the dynamics of slip during such events as shallow crustal faulting or mass movements

    Controlling proton-coupled electron transfer in bioinspired artificial photosynthetic relays

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    Bioinspired constructs consisting of benzimidazole-phenol moieties bearing N-phenylimines as proton-accepting substituents have been designed to mimic the H-bond network associated with the TyrZ-His190 redox relay in photosystem II. These compounds provide a platform to theoretically and experimentally explore and expand proton-coupled electron transfer (PCET) processes. The models feature H-bonds between the phenol and the nitrogen at the 3-position of the benzimidazole and between the 1H -benzimidazole proton and the imine nitrogen. Protonation of the benzimidazole and the imine can be unambiguously detected by infrared spectroelectrochemistry (IRSEC) upon oxidation of the phenol. DFT calculations and IRSEC results demonstrate that with sufficiently strong electron-donating groups at the para-position of the N-phenylimine group (e.g., -OCH3 substitution), proton transfer to the imine is exergonic upon phenol oxidation, leading to a one-electron, two-proton (E2PT) product with the imidazole acting as a proton relay. When transfer of the second proton is not sufficiently exergonic (e.g., -CN substitution), a one-electron, one-proton transfer (EPT) product is dominant. Thus, the extent of proton translocation along the H-bond network, either ~1.6 Å or ~6.4 Å, can be controlled through imine substitution. Moreover, the H-bond strength between the benzimidazole NH and the imine nitrogen, which is a function of their relative pKa values, and the redox potential of the phenoxyl radical/phenol couple are linearly correlated with the Hammett constants of the substituents. In all cases, a high potential (~1 V vs SCE) is observed for the phenoxyl radical/phenol couple. Designing and tuning redox-coupled proton wires is important for understanding bioenergetics and developing novel artificial photosynthetic systems.Fil: Odella, Emmanuel. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas; Argentina. Arizona State University; Estados Unidos. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; ArgentinaFil: Mora, Sabrina Jimena. Universidad Nacional de CĂłrdoba. Facultad de Ciencias QuĂ­micas. Departamento de QuĂ­mica OrgĂĄnica; Argentina. Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas; Argentina. Arizona State University; Estados UnidosFil: Wadsworth, Brian L.. Arizona State University; Estados UnidosFil: Huynh, Mioy T.. University of Yale; Estados UnidosFil: Goings, Joshua J.. University of Yale; Estados UnidosFil: Liddell, Paul A.. Arizona State University; Estados UnidosFil: Groy, Thomas L.. Arizona State University; Estados UnidosFil: Gervaldo, Miguel Andres. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Instituto de Investigaciones en TecnologĂ­as EnergĂ©ticas y Materiales Avanzados. - Consejo Nacional de Investigaciones CientĂ­ficas y TĂ©cnicas. Centro CientĂ­fico TecnolĂłgico Conicet - CĂłrdoba. Instituto de Investigaciones en TecnologĂ­as EnergĂ©ticas y Materiales Avanzados; ArgentinaFil: Sereno, Leonides Edmundo. Universidad Nacional de RĂ­o Cuarto. Facultad de Ciencias Exactas FisicoquĂ­micas y Naturales. Departamento de QuĂ­mica; ArgentinaFil: Gust, Devens. Arizona State University; Estados UnidosFil: Moore, Thomas A.. Arizona State University; Estados UnidosFil: Moore, Gary F.. Arizona State University; Estados UnidosFil: Hammes-Schiffer, Sharon. University of Yale; Estados UnidosFil: Moore, Ana L.. Arizona State University; Estados Unido

    Evolutionary paths to macrolide resistance in a Neisseria commensal converge on ribosomal genes through short sequence duplications

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    Neisseria commensals are an indisputable source of resistance for their pathogenic relatives. However, the evolutionary paths commensal species take to reduced susceptibility in this genus have been relatively underexplored. Here, we leverage in vitro selection as a powerful screen to identify the genetic adaptations that produce azithromycin resistance (ïżœ 2 ÎŒg/mL) in the Neisseria commensal, N. elongata. Across multiple lineages (n = 7/16), we find mutations that reduce susceptibility to azithromycin converge on the locus encoding the 50S ribosomal L34 protein (rpmH) and the intergenic region proximal to the 30S ribosomal S3 protein (rpsC) through short tandem duplication events. Interestingly, one of the laboratory evolved mutations in rpmH is identical (7LKRTYQ12), and two nearly identical, to those recently reported to contribute to high-level azithromycin resistance in N. gonorrhoeae. Transformations into the ancestral N. elongata lineage confirmed the causality of both rpmH and rpsC mutations. Though most lineages inheriting duplications suffered in vitro fitness costs, one variant showed no growth defect, suggesting the possibility that it may be sustained in natural populations. Ultimately, studies like this will be critical for predicting commensal alleles that could rapidly disseminate into pathogen populations via allelic exchange across recombinogenic microbial genera

    Energyscapes: linking the energy system and ecosystem services in real landscapes

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    The drive for sustainable energy production is leading to increased deployment of land based renewables. Although there is public support, in principle, for renewable energy at a national level, major resistance to renewable energy technologies often occurs at a local level. Within this context, it can be useful to consider the "energyscape" which we initially define as the complex spatial and temporal combination of the supply, demand and infrastructure for energy within a landscape. By starting with a consideration of the energyscape, we can then consider the positive and negative interactions with other ecosystem services within a particular landscape. This requires a multidisciplinary systems-approach that uses existing knowledge of landscapes, energy options, and the different perspectives of stakeholders. The approach is examined in relation to pilot case-study comprising a 155 km2 catchment in Bedfordshire, England

    Candidate chiral twin bands in the odd-odd nucleus 132 Cs : Exploring the limits of chirality in the mass A ≈ 130 region

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    High-spin states in the doubly odd N=77N=77 nucleus 132Cs{}^{132}\mathrm{Cs} have been studied. The known positive-parity structures have been extended. \ensuremath{\gamma}-ray linear-polarization and angular-correlation measurements have been performed to establish the spin and parity assignment of these structures. A new chiral partner of the \ensuremath{\pi}{h}_{11/2}\ensuremath{\bigotimes}\ensuremath{\nu}{h}_{11/2} band has been proposed. Three-dimensional tilted axis cranking model calculations have been performed and compared with the experimental results
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