Understanding transport mechanisms in ionic liquid/carbonate solvent electrolyte blends.

To unravel mechanistic details of the ion transport in liquid electrolytes, blends of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI), ethylene carbonate (EC) and dimethyl carbonate (DMC) with the conducting salts lithium hexafluorophosphate (LiPF6) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) were investigated as a function of the IL concentration. Electrochemical impedance, Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR) and Raman spectroscopy supported by Molecular Dynamics (MD) simulations allowed the structural and dynamic correlations of the ion motions to be probed. Remarkably, we identified that though the individual correlations among different ion types exhibit a clear concentration dependence, their net effect is nearly constant throughout the entire concentration range, resulting in approximately equal transport and transference numbers, despite a monitored cross-over from carbonate-based lithium coordination to a TFSI-based ion coordination. In addition, though dynamical ion correlation could be found, the absolute values of the ionic conductivity are essentially determined by the overall viscosity of the electrolyte. The IL/carbonate blends with a Pyr14TFSI fraction of ∼10 wt% are found to be promising electrolyte solvents, with ionic conductivities and lithium ion transference numbers comparable to those of standard carbonate-based electrolytes while the thermal and electrochemical stabilities are considerably improved. In contrast, the choice of the conducting salt only marginally affects the transport properties.

Induced coherence, vacuum fields, and complementarity in biphoton generation.

It is well established that spontaneous parametric down-conversion with induced coherence across two coupled interferometers results in high-visibility single-photon interference. We describe experiments in which additional photon channels are introduced such that "which-path" information is made possible and the fringe visibility in single-photon interference is reduced in accordance with basic notions of complementarity. However, these additional pathways result in nearly perfect visibility when photons are counted in coincidence. A simplified theoretical model accounts for these observations and attributes them directly to the vacuum fields at the different crystals.

Reactive molecular dynamics simulations of lithium-ion battery electrolyte degradation.

The development of reliable computational methods for novel battery materials has become essential due to the recently intensified research efforts on more sustainable energy storage materials. Here, we use a recently developed framework allowing to consistently incorporate quantum-mechanical activation barriers to classical molecular dynamics simulations to study the reductive solvent decomposition and formation of the solid electrolyte interphase for a graphite/carbonate electrolyte interface. We focus on deriving condensed-phase effective rates based on the elementary gas-phase reduction and decomposition energy barriers. After a short initial transient limited by the elementary barriers, we observe that the effective rate shows a transition to a kinetically slow regime influenced by the changing coordination environment and the ionic fluxes between the bulk electrolyte and the interface. We also discuss the impact of the decomposition on the ionic mobility. Thus, our work shows how elementary first-principles properties can be mechanistically leveraged to provide fundamental insights into electrochemical stability of battery electrolytes.

Characterisation of functional deficits induced by AAV overexpression of alpha-synuclein in rats.

Background: In the last decades different preclinical animal models of Parkinson's disease (PD) have been generated, aiming to mimic the progressive neuronal loss of midbrain dopaminergic (DA) cells as well as motor and non-motor impairment. Among all the available models, AAV-based models of human alpha-synuclein (h-aSYN) overexpression are promising tools for investigation of disease progression and therapeutic interventions. Objectives: The goal with this work was to characterise the impairment in motor and non-motor domains following nigrostriatal overexpression of h-aSYN and correlate the behavioural deficits with histological assessment of associated pathology. Methods: Intranigral injection of an AAV9 expressing h-aSYN was compared with untreated animals, 6-OHDA and AAV9 expressing either no transgene or GFP. The animals were assessed on a series of simple and complex behavioural tasks probing motor and non-motor domains. Post-mortem neuropathology was analysed using immunohistochemical methods. Results: Overexpression of h-aSYN led to progressive degeneration of DA neurons of the SN and axonal terminals in the striatum (STR). We observed extensive nigral and striatal pathology, resembling that of human PD brain, as well as the development of stable progressive deficit in simple motor tasks and in non-motor domains such as deficits in motivation and lateralised neglect. Conclusions: In the present work we characterized a rat model of PD that closely resembles human PD pathology at the histological and behavioural level. The correlation of cell loss with behavioural performance enables the selection of rats which can be used in neuroprotective or neurorestorative therapies.

[Odontoid fracture after high impact trauma : Assess instability correctly]. / Densfraktur nach Hochrasanztrauma : Instabilität richtig einschätzen.

Odontoid process fractures are frequent injuries of the cervical spine and usually occur at an advanced age and often due to minor trauma. In younger patients they are mainly observed in the context of high impact trauma. Odontoid fractures are classified according to Anderson and D'Alonzo. In rare cases the fracture results in cervical myelopathy, which can be life-threatening.In this article, two cases of patients with odontoid fractures and traumatic myelopathy are presented. The first case concerns a type III fracture, the second a type II fracture. In both cases the instability present was incorrectly assessed on the basis of the anatomical position in the initial computed tomography (CT). In the further course both cases showed considerable instability, which led to fatal spinal cord injuries.The purpose of this case report is to draw attention to the possible presence of spinal cord injuries in supposedly trivial odontoid fractures when high speed trauma has occurred. In particular, spinal cord compression should be considered in patients requiring resuscitation without having an internal medical cause. If the patient with a bone injury on CT, e.g. cannot be adequately assessed clinically by intubation, the indications for magnetic resonance imaging must be generously considered. This is the only way to ensure early detection of a myelopathy and timely treatment.

Lateralized deficits after unilateral AAV-vector based overexpression of alpha-synuclein in the midbrain of rats on drug-free behavioral tests.

BACKGROUND: Preclinical rodent models of Parkinson's aim to recapitulate some of the hallmarks of the disease as it presents in humans, including the progressive neuronal loss of dopaminergic neurons in the midbrain as well as the development of a behavioral phenotype. AAV vector-based models of alpha-synuclein overexpression are a promising tool to achieve such animal models with high face and predictive validity. OBJECTIVE: We have developed a preclinical rodent model of Parkinson's disease using an AAV-vector based overexpression of human alpha-synuclein. In the present work we characterize this model on a behavioral and histopathological level. METHODS: We use a AAV9 vector for transgene delivery to overexpress human alpha-synuclein under a CBA promoter. We compare the behavioral and histopathological changes to a AAV vector control group where the transgene was omitted and to that of a 6-OHDA lesion control. We assessed the behavioral performance of these three groups on a series of tests (Cylinder, Stepping, Corridor) at baseline and up to 22 weeks post-injection at which point we performed electrochemical recordings of dopamine kinetics. RESULTS: The overexpression of human alpha-synuclein led to the progressive manifestation of behavioral deficits on all three behavioral tests. This was accompanied with impaired dopamine release and reuptake kinetics as demonstrated by electrochemical detection methods. Histopathological quantifications corroborated the findings that we induced a moderate cell loss with remaining cells displaying pathological markers which are abundant in the brains of human PD patients. CONCLUSIONS: In the present work we developed a characterized a rat model of PD that closely mimics human disease development and pathology. Such model will be of great use for investigation of disease mechanisms and early therapeutic interventions.

The use of laser scanning confocal microscopy (LSCM) in materials science.

Laser scanning confocal microscopes are essential and ubiquitous tools in the biological, biochemical and biomedical sciences, and play a similar role to scanning electron microscopes in materials science. However, modern laser scanning confocal microscopes have a number of advantages for the study of materials, in addition to their obvious uses for high resolution reflected and transmitted light optical microscopy. In this paper, we provide several examples that exploit the laser scanning confocal microscope's capabilities of pseudo-infinite depth of field imaging, topographic imaging, photo-stimulated luminescence imaging and Raman spectroscopic imaging.

Planctopirus ephydatiae, a novel Planctomycete isolated from a freshwater sponge.

The microbiome of freshwater sponges is rarely studied, and not a single novel bacterial species has been isolated and subsequently characterized from a freshwater sponge to date. A previous study showed that 14.4% of the microbiome from Ephydatia fluviatilis belong to the phylum Planctomycetes. Therefore, we sampled an Ephydatia sponge from a freshwater lake and employed enrichment techniques targeting bacteria from the phylum Planctomycetes. The obtained strain spb1T was subject to genomic and phenomic characterization and found to represent a novel planctomycetal species proposed as Planctopirus ephydatiae sp. nov. (DSM 106606 = CECT 9866). In the process of differentiating spb1T from its next relative Planctopirus limnophila DSM 3776T, we identified and characterized the first phage - Planctopirus phage vB_PlimS_J1 - infecting planctomycetes that was only mentioned anecdotally before. Interestingly, classical chemotaxonomic methods would have failed to distinguish Planctopirus ephydatiae strain spb1T from Planctopirus limnophila DSM 3776T. Our findings demonstrate and underpin the need for whole genome-based taxonomy to detect and differentiate planctomycetal species.

Allende meteorite: a high-voltage electron petrographic study.

Electron-transparent sections of the Allende meteorite, a carbonaceous chondrite, have been prepared by ion-thinning and examined by high-voltage (800-kilovolt) transmission electron microscopy. The matrix crystals, mainly olivine, range in size from approximately 5 to approximately 0.01 micrometers; carbon is present as intergranular films of poorly crystalline graphite. The chondrules exhibit extensive radiation damage, a feature lacking in the matrix. In addition, both chondrules and matrix are undeformed and contain negative crystals; submicroscopic exsolution lamellae are present in pyroxenes. Comparison of the substructure in the Allende meteorite with that in the Parnallee meteorite and in lunar and selected terrestrial rocks leads to the conclusion that chondrule irradiation preceded cold accretion during formation of the solar system and that the meteorite has since been undisturbed.

High-voltage transmission electron microscopy study of lunar surface material.

The internal substructures of a type B sample have been examined at high magnification and compared with terrestrial rocks. Selected ultrathin sections were prepared from these multiphase materials by an ion-thinning technique and examined in a 1-Mev electron microscope, with complementary optical analyses. The structures in the ilmenite and plagioclase indicate that the lunar material has undergone plastic deformation by dislocation movement and possibly microtwinning, with subsequent recovery. The pyroxene exhibits complex lamellar structures of submicron spacing. These various observations are consistent with the optical microscopy evidence for distortion and recovery and identify the processes involved.

Shock-produced olivine glass: first observation.

Transmission electron microscope (TEM) observations of an experimentally shock-deformed single crystal of natural peridot, (Mg(0.88)Fe(0.12))(2)SiO(4), recovered from peak pressures of about 56 x 10(9) pascals revealed the presence of amorphous zones located within crystalline regions with a high density of tangled dislocations. This is the first reported observation of olivine glass. The shocked sample exhibits a wide variation in the degree of shock deformation on a small scale, and the glass appears to be intimately associated with the highest density of dislocations. This study suggests that olivine glass may be formed as a result of shock at pressures above about 50 to 55 x 10(9) pascals and that further TEM observations of naturally shocked olivines may demonstrate the presence of glass.

Innovative materials processing strategies: a biomimetic approach.

Many organisms construct structural ceramic (biomineral) composites from seemingly mundane materials; cell-mediated processes control both the nucleation and growth of mineral and the development of composite microarchitecture. Living systems fabricate biocomposites by: (i) confining biomineralization within specific subunit compartments; (ii) producing a specific mineral with defined crystal size and orientation; and (iii) packaging many incremental units together in a moving front process to form fully densified, macroscopic structures. By adapting biological principles, materials scientists are attempting to produce novel materials. To date, neither the elegance of the biomineral assembly mechanisms nor the intricate composite microarchitectures have been duplicated by nonbiological processing. However, substantial progress has been made in the understanding of how biomineralization occurs, and the first steps are now being taken to exploit the basic principles involved.

Measuring the excitations in a new S = 1/2 quantum spin chain material with competing interactions.

Recently a new one-dimensional (1D) quantum spin chain system has been reported: catena-dichloro(2-Cl-3Mpy)copper(II), (where 2-Cl-3Mpy=2-chloro-3-methylpyridine). Preliminary calculations and bulk magnetic property measurements indicate that this system does not undergo magnetic ordering down to 1.8 K and is a prime candidate for investigating frustration in a J 1/J 2 system (where the nearest neighbour interactions, J 1, are ferromagnetic and the next nearest neighbour interactions, J 2, are antiferromagnetic). Calculations predicted three possible magnetic interaction strengths for J 1 below 6 meV depending on the orientation of the ligand. For one of the predicted J 1 values, the existence of a quantum critical point is implied. A deuterated sample of catena-dichloro(2-Cl-3Mpy)copper(II) was synthesised and the excitations measured using inelastic neutron scattering. Scattering indicated the most likely scenario involves spin-chains where each chain consists of only one of the three possible magnetic excitations in this material, rather than the completely random array of exchange interactions within each chain as predicted by Herringer et al (2014 Chem. Eur. J. 20 8355-62). This indicates the possibility of tuning the chemical structure to favour a system which may exhibit a quantum critical point.

Microscopic description of the low-temperature anomalies in silica and lithium silicate via computer simulations.

Information about the nature of the low-temperature anomalies and in particular the properties of the tunneling systems in silica and lithium silica glasses are revealed via computer simulations. The potential energy landscape of these systems is systematically explored for adjacent pairs of local minima which may act as double-well potentials (DWPs) at low temperatures. Three different types of DWPs are distinguished, related to perfectly coordinated silica, intrinsic silica defects, and extrinsic defects. Their properties such as the spatial extension and the dipole moment are characterized in detail. Furthermore, the absolute number of tunneling systems, that is, symmetric DWPs, is estimated. The results are compared with dielectric echo, specific heat, and acoustic experiments on Suprasil I and Suprasil W. A semiquantitative agreement for all relevant features is obtained.

Origin of the decoupling of oxygen and silicon dynamics in liquid silica as expressed by its potential energy landscape.

The oxygen and silicon dynamics in silica are compared via computer simulations. In agreement with experimental data and previous simulations a decoupling of oxygen and silicon dynamics is observed upon cooling. The origin of this decoupling is studied in the framework of the potential energy landscape. From analysis of the transition features between neighboring superstructures of minima, denoted metabasins, the differences between the oxygen and silicon dynamics can be quantified. The decoupling can be explicitly related to the presence of generalized rotational processes, giving rise to oxygen but not to silicon displacement. Closer analysis of these processes yields important insight into the nature of the potential energy landscape of silica. The physical picture of relaxation processes in silica, obtained in previous work for oxygen dynamics, is consistent with decoupling effects, elucidated here.

Dynamics of liquid silica as explained by properties of the potential energy landscape.

The dynamics of silica displays an Arrhenius temperature dependence, classifying silica as a strong glass-former. Using recently developed concepts to analyze the potential energy landscape, one can get a far-reaching understanding of the long-range transport of silica. It can be expressed in terms of properties of the thermodynamics as well as local relaxation processes, thereby extending the phenomenological standard picture of a strong glass-former. The local relaxation processes are characterized by complex correlated sequences of bond breaking and reformation processes.

Potential-energy landscape of a supercooled liquid and its resemblance to a collection of traps.

It is analyzed whether the potential energy landscape of a glass-forming system can be effectively mapped on a random model which is described in statistical terms. For this purpose we generalize the simple trap model of Monthus and Bouchaud [J. Phys. A 29, 3847 (1996)] by dividing the total system into M weakly interacting identical subsystems, each being described in terms of a trap model. The distribution of traps in this extended trap model (ETM) is fully determined by the thermodynamics of the glass former. The dynamics is described by two adjustable parameters, one characterizing the common energy level of the barriers, the other the strength of the interaction. The comparison is performed for the standard binary mixture Lennard-Jones system with 65 particles. The metabasins, identified in our previous work, are chosen as traps. Comparing molecular dynamics simulations of the Lennard-Jones system with Monte Carlo calculations of the ETM allows one to determine the adjustable parameters. Analysis of the first moment of the waiting distribution yields an optimum agreement when choosing M approximately 3 subsystems. Comparison with the second moment of the waiting time distribution, reflecting dynamic heterogeneities, indicates that the sizes of the subsystems may fluctuate.

Distinct iron architecture in SF3B1-mutant myelodysplastic syndrome patients is linked to an SLC25A37 splice variant with a retained intron.

Perturbation in iron homeostasis is a hallmark of some hematologic diseases. Abnormal sideroblasts with accumulation of iron in the mitochondria are named ring sideroblasts (RS). RS is a cardinal feature of refractory anemia with RS (RARS) and RARS with marked thrombocytosis (RARS/-T). Mutations in SF3B1, a member of the RNA splicing machinery are frequent in RARS/-T and defects of this gene were linked to RS formation. Here we showcase the differences in iron architecture of SF3B1-mutant and wild-type (WT) RARS/-T and provide new mechanistic insights by which SF3B1 mutations lead to differences in iron. We found higher iron levels in SF3B1 mutant vs WT RARS/-T by transmission electron microscopy/spectroscopy/flow cytometry. SF3B1 mutations led to increased iron without changing the valence as shown by the presence of Fe(2+) in mutant and WT. Reactive oxygen species and DNA damage were not increased in SF3B1-mutant patients. RNA-sequencing and Reverse transcriptase PCR showed higher expression of a specific isoform of SLC25A37 in SF3B1-mutant patients, a crucial importer of Fe(2+) into the mitochondria. Our studies suggest that SF3B1 mutations contribute to cellular iron overload in RARS/-T by deregulating SLC25A37.

Crystallization studies on avian eggshell membranes: implications for the molecular factors controlling eggshell formation.

The avian eggshell is a natural biopolymer and mineral composite. It is a very useful model for biomimetic mineralization, since it is among the fastest forming hard tissues known. Isolated eggshell membranes, which were demineralized in vitro, were used to investigate the in vitro modulation of CaCO3 crystal deposition by organic matrix materials. Crystallization on the demineralized eggshell membrane occurred almost exclusively at the peripheries of residual calcium reserve assemblies, which contain a high concentration of sulfur. Similar structures are observed for eggshell membranes after natural demineralization. The characteristic rhombohedral crystal morphologies of the calcite crystals grown in this in vitro system are much less regular when grown in the presence of organic matrix or partially purified dermatan sulfate proteoglycans obtained from the eggshell. The effect of these macromolecules on the morphology and size of CaCO3 crystals is concentration-dependent. These studies indicate the complexity of the molecular and ionic interactions involved in the initiation and formation of the eggshell, with the focus on the role of the organic matrix.