Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H₂, pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H₂ concentrations were heterogeneous at the microscale (<500-1000 μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H₂ under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L_III-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state.     

On stochastic comparisons of finite mixtures for some semiparametric families of distributions

In this paper, we consider the classical finite mixture model, which is an effective tool for modeling lifetime distributions for random samples from heterogeneous populations. We discuss new results on stochastic comparison for two finite mixtures when each of them is drawn from one of the following semiparametric families, i.e., proportional hazards, accelerated lifetime and proportional reversed hazards.     

Quartz resonator instabilities under cryogenic conditions

The phase noise of a quartz crystal resonator working at liquid helium temperatures is studied. Measurement methods and the device environment are explained. The phase noise is measured for different resonance modes, excitation levels, amount of operating time, device orientations in relation to the cryocooler vibration axis, and temperatures. Stability limits of a frequency source based on such devices are evaluated in the present measurement conditions. The sources of phase flicker and white noises are identified. Finally, the results are compared with previous works.     

Three-layer flow membrane system on a microchip for investigation of molecular transport

A stable three-layer flow system, water/organic solvent/water, has been successfully applied for the first time in a microchannel to get rapid transport through an organic liquid membrane. In the continuous laminar flow region, the analyte (methyl red) was rapidly extracted across the microchannel from the donor to the acceptor phase through the organic solvent phase (cyclohexane). Thermal lens microscopy was used to monitor the process. The thickness of the organic phase, sandwiched by the two aqueous phases, was approximately 64 microm, and it was considered as a thin liquid organic membrane. Permeability studies showed the effects of molecular diffusion, layer thickness, and organic solvent-water partition coefficient on the molecular transport. In the microchip, complete equilibration was achieved in several seconds, in contrast to a conventionally used apparatus, where it takes tens of minutes. The thickness of the organic and aqueous boundary layers was defined as equal to the microchannel dimensions, and the organic solvent-water partition coefficient was determined on a microchip using the liquid/liquid extraction system. Experimental data on molecular transport across the organic membrane were in agreement with the calculated permeability based on the three-compartment water/organic solvent/water model. This kind of experiment can be performed only in a microspace, and the system can be considered as a potential biological membrane for future in vitro study of drug transport.     

Uncovering the Potential of M1-Site-Activated NASICON Cathodes for Zn-Ion Batteries

There is a long-standing consciousness that the rhombohedral NASICON-type compounds as promising cathodes for Li⁺/Na⁺ batteries should have inactive M1(6b) sites with ion (de)intercalation occurring only in the M2 (18e) sites. Of particular significance is that M1 sites active for charge/discharge are commonly considered undesirable because the ion diffusion tends to be disrupted by the irregular occupation of channels, which accelerates the deterioration of battery. However, it is found that the structural stability can be substantially improved by the mixed occupation of Na⁺/Zn²⁺ at both M1 and M2 when using NaV₂(PO₄)₃ (NVP) as a cathode for Zn-ion batteries. The results of atomic-scale scanning transmission electron microscopy, analysis of ab initio molecular dynamics simulations, and an accurate bond-valence-based structural model reveal that the improvement is due to the facile migration of Zn²⁺ in NVP, which is enabled by a concerted Na⁺/Zn²⁺ transfer mechanism. In addition, significant improvement of the electronic conductivity and mechanical properties is achieved in Zn²⁺-intercalated ZnNaV₂(PO₄)₃ in comparison with those of Na₃V₂(PO₄)₃. This work not only provides in-depth insight into Zn²⁺ intercalation and dynamics in NVP unlocked by activating the M1 sites, but also opens a new route toward design of improved NASICON cathodes.     

Polaronic Trions at the MoS2/SrTiO3 Interface

The reduced electrical screening in 2D materials provides an ideal platform for realization of exotic quasiparticles, that are robust and whose functionalities can be exploited for future electronic, optoelectronic, and valleytronic applications. Recent examples include an interlayer exciton, where an electron from one layer binds with a hole from another, and a Holstein polaron, formed by an electron dressed by a sea of phonons. Here, a new quasiparticle is reported, “polaronic trion” in a heterostructure of MoS₂/SrTiO₃ (STO). This emerges as the Fröhlich bound state of the trion in the atomically thin monolayer of MoS₂ and the very unique low energy soft phonon mode (≤7 meV, which is temperature and field tunable) in the quantum paraelectric substrate STO, arising below its structural antiferrodistortive (AFD) phase transition temperature. This dressing of the trion with soft phonons manifests in an anomalous temperature dependence of photoluminescence emission leading to a huge enhancement of the trion binding energy (≈70 meV). The soft phonons in STO are sensitive to electric field, which enables field control of the interfacial trion–phonon coupling and resultant polaronic trion binding energy. Polaronic trions could provide a platform to realize quasiparticle‐based tunable optoelectronic applications driven by many body effects.     

Vapor condensation upon transversal flow around a cylinder (boundary heat-exchange laws)

The problem of vapor condensation upon transversal flow around a horizontal cylinder is considered. The analytical solutions for the “boundary heat-exchange laws” are obtained. The solutions show the dependence of the heat transfer coefficient on the corresponding factor (gravity, interfacial friction, longitudinal pressure gradient) under the assumption that there is no effect of other factors. The boundary laws obtained for moving vapor are shown to depend on pressure in the same manner, while the temperature differential has different effects in specified asymptotics. The theoretical results obtained are used for qualitative analysis of the available experimental data.     

The incorporation of mono- and bi-functionalized multiwall carbon nanotubes in organic photovoltaic cells

We have successfully prepared mono- and bi-functionalized multiwall carbon nanotubes (MWCNT) with thiophene, amine and thiophene-amine groups. The dispersion of nanotubes has been enhanced and stable optimized dispersions in organic solvents were obtained. These functionalized nanotubes have been successfully incorporated into bulk heterojunction (BHJ) organic photovoltaic (OPV) cells with a poly (3-hexyl thiophene) (P3HT) and [6, 6]-phenyl-C(61)-butyric acid methyl ester (PCBM) photoactive blended layer. The incorporation of MWCNT with different functional groups, in the active layer, results in different cell performance with respect to a reference cell. A maximum power conversion efficiency of 2.5% is achieved with the inclusion of thiophene functionalized nanotubes. This improvement in the device performance is attributed to an extension of the exciton dissociation volume and charge transport properties through the nanotube percolation network in P3HT/CNT, PCBM/CNT or both phases. This is believed to be due to more efficient dispersion of the functionalized nanotubes within the photoactive composite layer.     

Non-homogeneous extracellular resistivity affects the current-source density profiles of up-down state oscillations

Rhythmic local field potential (LFP) oscillations observed during deep sleep are the result of synchronized electrical activities of large neuronal ensembles, which consist of alternating periods of activity and silence, termed 'up' and 'down' states, respectively. Current-source density (CSD) analysis indicates that the up states of these slow oscillations are associated with current sources in superficial cortical layers and sinks in deep layers, while the down states display the opposite pattern of source-sink distribution. We show here that a network model of up and down states displays this CSD profile only if a frequency-filtering extracellular medium is assumed. When frequency filtering was modelled as inhomogeneous conductivity, this simple model had considerably more power in slow frequencies, resulting in significant differences in LFP and CSD profiles compared with the constant-resistivity model. These results suggest that the frequency-filtering properties of extracellular media may have important consequences for the interpretation of the results of CSD analysis.