Macroscopic changes in aquaporin-4 underlie blast traumatic brain injury-related impairment in glymphatic function.

Mild traumatic brain injury (mTBI) has emerged as a potential risk factor for the development of neurodegenerative conditions such as Alzheimer's disease and chronic traumatic encephalopathy. Blast mTBI, caused by exposure to a pressure wave from an explosion, is predominantly experienced by military personnel and has increased in prevalence and severity in recent decades. Yet the underlying pathology of blast mTBI is largely unknown. We examined the expression and localization of AQP4 in human post-mortem frontal cortex and observed distinct laminar differences in AQP4 expression following blast exposure. We also observed similar laminar changes in AQP4 expression and localization and delayed impairment of glymphatic function that emerged 28 days following blast injury in a mouse model of repetitive blast mTBI. In a cohort of veterans with blast mTBI, we observed that blast exposure was associated with an increased burden of frontal cortical MRI-visible perivascular spaces, a putative neuroimaging marker of glymphatic perivascular dysfunction. These findings suggest that changes in AQP4 and delayed glymphatic impairment following blast injury may render the post-traumatic brain vulnerable to post-concussive symptoms and chronic neurodegeneration.

Editorial Commentary: Arthroscopy Is the Gold Standard for Diagnosis of Meniscal Ramp Lesions: Magnetic Resonance Imaging Also May Be Helpful.

Identifying and treating medial meniscal ramp lesions in conjunction with ligament reconstruction restores critical stability in knees with ligament injuries. This must begin with obtaining high-quality magnetic resonance imaging (MRI) and critical evaluation of the MRI and include a subsequent thorough arthroscopic examination of these knees. As evident in previous studies, most surgeons associate medial meniscal ramp lesions with anterior cruciate ligament (ACL) tears. Biomechanical studies have reported that a ramp lesion produces significant anterior tibial translation and external rotational instability in ACL-deficient knees that is not reestablished with an isolated ACL reconstruction. In addition, recent research identified ramp lesions in one-third of multiligament knee injuries with an intact ACL and two-thirds of patients with posteromedial tibial plateau bone bruises on MRI. Restoring knee stability and biomechanics is necessary in treating all knee ligament injuries. Don't miss the meniscal ramp lesion. Have a high index of suspicion, obtain a high-quality MRI,and arthroscopically evaluate the meniscocapsular junction of the medial meniscus, especially if there is a bone bruise seen on MRI.

Bulky and Stable Copper(I)-Phenanthroline Complex: Impact of Steric Strain and Symmetry on the Excited-State Properties.

The steric strain around copper(I) in typical [Cu(NNR)2]+ complexes, where NNR is a diimine ligand substituted in α-positions of the nitrogen atoms by R, is known to strongly impact the excited-state properties. Generally speaking, the larger the R, the longer the emission lifetime and the higher the quantum yield. However, the stability of the coordination scaffold can be at stake if the steric strain imposed by R is too large. In this work, we explore a way of fine-tuning the steric strain around Cu(I) to reach a balance between high emission quantum yield and stability in a highly bulky copper(I) complex. Taking stable [Cu(dipp)2]+ and unstable [Cu(dtbp)2]+ (where dipp and dtbp are, respectively, 2,9-diisopropyl-1,10-phenanthroline and 2,9-di-tert-butyl-1,10-phenanthroline) as the boundary of two least and most sterically strained structures, we designed and characterized the nonsymmetrical ligand 2-isopropyl-9-tert-butyl-1,10-phenanthroline (L1) and corresponding complex [Cu(L1)2]+ (Cu1). The key experimental findings are that Cu1 exhibits a rigid tetrahedral geometry in the ground state, close to that of [Cu(dtbp)2]+ and with an intermediate stability between that of [Cu(dipp)2]+ and [Cu(dtbp)2]+. Conversely, the nonsymmetrical nature of ligand L1 leads to a shorter emission lifetime and smaller quantum yield than those of either [Cu(dipp)2]+ or [Cu(dtbp)2]+. This peculiar behavior is rationalized through the in depth analysis of the ultrafast dynamics of the excited state measured with optical transient absorption spectroscopy and theoretical calculations performed on the ground and excited state of Cu1. Our main findings are that the obtained complex is significantly more stable than [Cu(dtbp)2]+ despite the sterically strained coordination sphere. The nonsymmetrical nature of the ligand translates into a strongly distorted structure in the excited state. The distortion can be described as a rocking motion of one ligand, entailing the premature extinction of the excited state via several deactivation channels.

Harnessing Intermolecular Interactions to Promote Long-Lived Photoinduced Charge Separation from Copper Phenanthroline Chromophores.

Facilitating photoinduced electron transfer (PET) while minimizing rapid charge-recombination processes to produce a long-lived charge-separated (CS) state represents a primary challenge associated with achieving efficient solar fuel production. Natural photosynthetic systems employ intermolecular interactions to arrange the electron-transfer relay in reaction centers and promote a directional flow of electrons. This work explores a similar tactic through the synthesis and ground- and excited-state characterization of two Cu(I)bis(phenanthroline) chromophores with homoleptic and heteroleptic coordination geometries and which are functionalized with negatively charged sulfonate groups. The addition of sulfonate groups enables solubility in pure water, and it also induces assembly with the dicationic electron acceptor methyl viologen (MV2+) via bimolecular, dynamic electrostatic interactions. The effect of the sulfonate groups on the ground- and excited-state properties was evaluated by comparison with the unsulfonated analogues in 1:1 acetonitrile/water. The excited-state lifetimes for all sulfonated complexes are similar to what we expect from previous literature, with the exception of the sulfonated heteroleptic complex whose metal-to-ligand charge-transfer (MLCT) lifetime in water has two components that are fit to 10 and 77 ns. For the sulfonated complexes, we detected reduced MV+• in both solvent environments following MLCT excitation, but control measurements in 1:1 acetonitrile/water with the unsulfonated analogues showed no PET to MV2+, indicating that electrostatically driven supramolecular assemblies of the sulfonated complexes with MV2+ facilitate the observed PET. Additionally, the strength of the intermolecular interactions driving the formation of these assemblies changes drastically with the solvent environment. In 1:1 acetonitrile/water, PET occurred from both sulfonated complexes with quantum yields (ΦET) of 2-3% but increased to a remarkable 98% for the sulfonated heteroleptic complex with a 3 µs CS-state lifetime in water.

Global biogeochemical cycle of vanadium.

Synthesizing published data, we provide a quantitative summary of the global biogeochemical cycle of vanadium (V), including both human-derived and natural fluxes. Through mining of V ores (130 × 109 g V/y) and extraction and combustion of fossil fuels (600 × 109 g V/y), humans are the predominant force in the geochemical cycle of V at Earth's surface. Human emissions of V to the atmosphere are now likely to exceed background emissions by as much as a factor of 1.7, and, presumably, we have altered the deposition of V from the atmosphere by a similar amount. Excessive V in air and water has potential, but poorly documented, consequences for human health. Much of the atmospheric flux probably derives from emissions from the combustion of fossil fuels, but the magnitude of this flux depends on the type of fuel, with relatively low emissions from coal and higher contributions from heavy crude oils, tar sands bitumen, and petroleum coke. Increasing interest in petroleum derived from unconventional deposits is likely to lead to greater emissions of V to the atmosphere in the near future. Our analysis further suggests that the flux of V in rivers has been incremented by about 15% from human activities. Overall, the budget of dissolved V in the oceans is remarkably well balanced-with about 40 × 109 g V/y to 50 × 109 g V/y inputs and outputs, and a mean residence time for dissolved V in seawater of about 130,000 y with respect to inputs from rivers.

Photoinduced Plasmon-Driven Chemistry in trans-1,2-Bis(4-pyridyl)ethylene Gold Nanosphere Oligomers.

Continuous wave (CW) pump-probe surface-enhanced Raman spectroscopy (SERS) is used to examine a range of plasmon-driven chemical behavior in the molecular SERS signal of trans-1,2-bis(4-pyridyl)ethylene (BPE) adsorbed on individual Au nanosphere oligomers (viz., dimers, trimers, tetramers, etc.). Well-defined new transient modes are caused by high fluence CW pumping at 532 nm and are monitored on the seconds time scale using a low intensity CW probe field at 785 nm. Comparison of time-dependent density functional theory (TD-DFT) calculations with the experimental data leads to the conclusion that three independent chemical processes are operative: (1) plasmon-driven electron transfer to form the BPE anion radical; (2) BPE hopping between two adsorption sites; and (3) trans-to- cis-BPE isomerization. Resonance Raman and electron paramagnetic resonance (EPR) spectroscopy measurements provide further substantiation for the observation of an anion radical species formed via a plasmon-driven electron transfer reaction. Applications of these findings will greatly impact the design of novel plasmonic devices with the future ability to harness new and efficient energetic pathways for both chemical transformation and photocatalysis at the nanoscale level.

Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4'-Bipyridine Gold Nanosphere Oligomers.

We clarify mechanistic questions regarding plasmon-driven chemistry and nanoscale photocatalysis within optically confined near-field plasmonic systems. Using surface-enhanced Raman scattering (SERS), we directly monitor the photoinduced reaction dynamics of 4,4'-bipyridine molecules, localized in plasmonic hot spots within individual gold nanosphere oligomers. Our experiment generates surface electrons from the gold nanoparticle using an intense off-molecular resonance continuous wave pump field, and detects radical anion products via SERS. This is done by adopting a dual-wavelength spectroscopic approach. Empirical evidence of plasmon-driven electron transfer is provided for the first time by direct detection of the 4,4'-bipyridine radical anion species localized in the plasmonic hot spots of individual gold nanosphere oligomers, corroborated by open-shell density functional theory calculations. An isotopologue approach using both protonated and deuterated 4,4'-bipyridine molecules demonstrates the single molecule response of plasmon-driven electron transfer occurring in single nanosphere oligomer systems with a 3% yield, a phenomenon unobserved in ensemble measurements under analogous experimental conditions. This mechanism has broad applicability to using nanoscale chemical reactors for surface redox reactions on the subnanometer scale.

Plasmon resonance dynamics and enhancement effects in tris(2,2'-bipyridine)ruthenium(II) gold nanosphere oligomers.

Ruthenium-based metal complexes are one of the most widely studied dyes because of their rich photochemistry and light-harvesting properties. Significant attention has been paid to the energy and charge transfer dynamics of these dyes on semiconductor substrates. However, studies on photophysical and photochemical properties of these dyes in plasmonic environments are rare. In this study, we report a plasmon-mediated resonance energy transfer in an optimized oligomer system that enhances the photoexcited population of the well known dye, tris(2,2'-bipyridine)ruthenium(II), [Ru(BPY)3]2+ adsorbed on gold nanosphere surfaces with a defluorescenced Raman signal. Structural and chemical information is collected using a range of techniques that include in situ time-resolved UV/VIS, DLS, SERS, and TA. The findings have great potential to impact nanoscience broadly with special emphasis on surface photocatalysis, redox chemistry, and solar energy harvesting.

Aluminum foil negative electrodes with multiphase microstructure for all-solid-state Li-ion batteries.

Metal negative electrodes that alloy with lithium have high theoretical charge storage capacity and are ideal candidates for developing high-energy rechargeable batteries. However, such electrode materials show limited reversibility in Li-ion batteries with standard non-aqueous liquid electrolyte solutions. To circumvent this issue, here we report the use of non-pre-lithiated aluminum-foil-based negative electrodes with engineered microstructures in an all-solid-state Li-ion cell configuration. When a 30-µm-thick Al94.5In5.5 negative electrode is combined with a Li6PS5Cl solid-state electrolyte and a LiNi0.6Mn0.2Co0.2O2-based positive electrode, lab-scale cells deliver hundreds of stable cycles with practically relevant areal capacities at high current densities (6.5 mA cm-2). We also demonstrate that the multiphase Al-In microstructure enables improved rate behavior and enhanced reversibility due to the distributed LiIn network within the aluminum matrix. These results demonstrate the possibility of improved all-solid-state batteries via metallurgical design of negative electrodes while simplifying manufacturing processes.

A Rare Case of Pyrethroid Poisoning Presenting as Auditory Hallucination.

Pyrethroid is an insecticide which is widely used for household pests. Even though they are relatively less toxic to humans, reports of accidental poisoning are not uncommon. Cases of anosmia, tremors and arrhythmias after pyrethroid exposure have been reported; however auditory hallucinations have not been presented yet. Herein, we present a case of auditory hallucination in the form of ringing in the ear after exposure to airborne pyrethrin in a 69-year-old male. The significance of this case report is related to the wide use of insecticides containing pyrethrin and highlights the need for physician awareness of this uncommon pathology.

Role of Areal Capacity in Determining Short Circuiting of Sulfide-Based Solid-State Batteries.

Solid-state batteries (SSBs) with lithium metal anodes offer higher specific energy than conventional lithium-ion batteries, but they must utilize areal capacities >3 mAh cm-2 and cycle at current densities >3 mA cm-2 to achieve commercial viability. Substantial research effort has focused on increasing the rate capabilities of SSBs by mitigating detrimental processes such as lithium filament penetration and short circuiting. Less attention has been paid to understanding how areal capacity impacts lithium plating/stripping behavior in SSBs, despite the importance of areal capacity for achieving high specific energy. Here, we investigate and quantify the relationships among areal capacity, current density, and plating/stripping stability using both symmetric and full-cell configurations with a sulfide solid-state electrolyte (Li6PS5Cl). We show that unstable deposition and short circuiting readily occur at rates much lower than the measured critical current density when a sufficient areal capacity is passed. A systematic study of continuous plating under different electrochemical conditions reveals average "threshold capacity" values at different current densities, beyond which short circuiting occurs. Cycling cells below this threshold capacity significantly enhances cell lifetime, enabling stable symmetric cell cycling at 2.2 mA cm-2 without short circuiting. Finally, we show that full cells with LiNi0.8Mn0.1Co0.1O2 also exhibit threshold capacity behavior, but they tend to short circuit at lower current densities and areal capacities. Our results quantify the effects of transferred capacity and demonstrate the importance of using realistic areal capacities in experiments to develop viable solid-state batteries.

Counter-rotating microplates at the Galapagos triple junction.

An 'incipient' spreading centre east of (and orthogonal to) the East Pacific Rise at 2 degrees 40' N has been identified as forming a portion of the northern boundary of the Galapagos microplate. This spreading centre was described as a slowly diverging, westward propagating rift, tapering towards the East Pacific Rise. Here we present evidence that the 'incipient rift' has also rifted towards the east and opens anticlockwise about a pivot at its eastern end. The 'incipient rift' then bounds a second microplate, north of the clockwise-rotating Galapagos microplate. The Galapagos triple junction region, in the eastern equatorial Pacific Ocean, thus consists of two counter-rotating microplates partly separated by the Hess Deep rift. Our kinematic solution for microplate motion relative to the major plates indicates that the two counter-rotating microplates may be treated as rigid blocks driven by drag on the microplates' edges3.

Accelerating Rate Calorimetry and Complementary Techniques to Characterize Battery Safety Hazards.

The hazards associated with lithium-based battery chemistries are well-documented due to their catastrophic nature. Risk is typically qualitatively assessed through an engineering risk matrix. Within the matrix, potentially hazardous events are categorized and ranked in terms of severity and probability to provide situational awareness to decision makers and stakeholders. The stochastic nature of battery failures, particularly the lithium-ion chemistry, makes the probability axis of a matrix difficult to properly assess. Fortunately, characterization tools exist, such as accelerated rate calorimetry (ARC), that characterize degrees of battery failure severity. ARC has been used extensively to characterize reactive chemicals but can provide a new application to induce battery failures under safe, controlled experimental conditions and quantify critical safety parameters. Due to the robust nature of the extended volume calorimeter, cells may be safely taken to failure due to a variety of abuses: thermal (simple heating of cell), electrochemical (overcharge), electrical (external short circuit), or physical (crush or nail penetration). This article describes the procedures to prepare and instrument a commercial lithium-ion battery cell for failure in an ARC to collect valuable safety data: onset of thermal runaway, endotherm associated with polymer separator melting, pressure release during thermal runaway, gaseous collection for analytical characterization, maximum temperature of complete reaction, and visual observation of decomposition processes using a high temperature borescope (venting and cell can breach). A thermal "heat-wait-seek" method is used to induce cell failure, in which the battery is heated incrementally to a set point, then the instrument identifies heat generation from the battery. As heat generates a temperature rise in the battery, the calorimeter temperature follows this temperature rise, maintaining an adiabatic condition. Therefore, the cell does not exchange heat with the external environment, so all heat generation from the battery under failure is captured.

Comparing feedback and spatial approaches to advance ecosystem-based fisheries management in a changing Antarctic.

To implement ecosystem-based approaches to fisheries management, decision makers need insight on the potential costs and benefits of the policy options available to them. In the Southern Ocean, two such options for addressing trade-offs between krill-dependent predators and the krill fishery include "feedback management" (FBM) strategies and marine protected areas (MPAs); in theory, the first adjusts to change, while the latter is robust to change. We compared two possible FBM options to a proposed MPA in the Antarctic Peninsula and Scotia Sea given a changing climate. One of our feedback options, based on the density of Antarctic krill (Euphasia superba), projected modest increases in the abundances of some populations of krill predators, whereas outcomes from our second FBM option, based on changes in the abundances of penguins, were more mixed, with some areas projecting predator population declines. The MPA resulted in greater increases in some, but not all, predator populations than either feedback strategy. We conclude that these differing outcomes relate to the ways the options separate fishing and predator foraging, either by continually shifting the spatial distribution of fishing away from potentially vulnerable populations (FBM) or by permanently closing areas to fishing (the MPA). For the krill fishery, we show that total catches could be maintained using an FBM approach or slightly increased with the MPA, but the fishery would be forced to adjust fishing locations and sometimes fish in areas of relatively low krill density-both potentially significant costs. Our work demonstrates the potential to shift, rather than avoid, ecological risks and the likely costs of fishing, indicating trade-offs for decision makers to consider.

What's the catch? Profiling the benefits and costs associated with marine protected areas and displaced fishing in the Scotia Sea.

Both costs and benefits must be considered when implementing marine protected areas (MPAs), particularly those associated with fishing effort displaced by potential closures. The Southern Ocean offers a case study in understanding such tradeoffs, where MPAs are actively being discussed to achieve a range of protection and sustainable use objectives. Here, we evaluated the possible impacts of two MPA scenarios on the Antarctic krill (Euphausia superba) fishery and krill-dependent predators in the Scotia Sea, explicitly addressing the displacement of fishing from closed areas. For both scenarios, we employed a minimally realistic, spatially explicit ecosystem model and considered three alternative redistributions of displaced fishing. We projected both MPAs to provide positive outcomes for many krill-dependent predators, especially when closed areas included at least 50-75% of their foraging distributions. Further, differences between the scenarios suggest ways to improve seal and penguin protection in the Scotia Sea. MPA scenarios also projected increases in total fishery yields, but alongside risks of fishing in areas where relatively low krill densities could cause the fishery to suspend operations. The three alternatives for redistributing displaced fishing had little effect on benefits to predators, but did matter for the fishery, with greater differences in overall catch and risk of fishing in areas of low krill density when displaced fishing was redistributed evenly among the open areas. Collectively, results suggest a well-designed MPA in the Scotia Sea may protect krill-dependent predators, even with displaced fishing, and preclude further spatial management of the krill fishery outside the MPA. More broadly, outcomes denote the importance of delineating fishing and predator habitat, spatial scales, and the critical trade-offs inherent in MPA development.

Surface immobilized copper(I) diimine photosensitizers as molecular probes for elucidating the effects of confinement at interfaces for solar energy conversion.

Heteroleptic copper(i) bis(phenanthroline) complexes with surface anchoring carboxylate groups have been synthesized and immobilized on nanoporous metal oxide substrates. The species investigated are responsive to the external environment and this work provides a new strategy to control charge transfer processes for efficient solar energy conversion.

Ordinal judgments of symbolic stimuli by capuchin monkeys (Cebus apella) and rhesus monkeys (Macaca mulatta): the effects of differential and nondifferential reward.

Ordinal learning was investigated in capuchin monkeys (Cebus apella) and rhesus monkeys (Macaca mulatta). In Experiment 1, both species were presented with pairings of the Arabic numerals 0 to 9. Some monkeys were given food rewards equal to the value of the numeral selected and some were rewarded with a single pellet only for choosing the higher numeral within the pair. Both species learned to select the larger numeral, but only rhesus monkeys that were differentially rewarded performed above chance levels when presented with novel probe pairings. In Experiment 2, the monkeys were first presented with arrays of 5 familiar numerals (from the range 0 to 9) and then arrays of 5 novel letters (from the range A to J) with the same reward outcomes in place as in Experiment 1. Both species performed better with the numerals, suggesting that an ordinal sequence of all stimuli had been learned during Experiment 1, rather than a matrix of two-choice discriminations.

Impacts of rising sea temperature on krill increase risks for predators in the Scotia Sea.

Climate change is a threat to marine ecosystems and the services they provide, and reducing fishing pressure is one option for mitigating the overall consequences for marine biota. We used a minimally realistic ecosystem model to examine how projected effects of ocean warming on the growth of Antarctic krill, Euphausia superba, might affect populations of krill and dependent predators (whales, penguins, seals, and fish) in the Scotia Sea. We also investigated the potential to mitigate depletion risk for predators by curtailing krill fishing at different points in the 21st century. The projected effects of ocean warming on krill biomass were strongest in the northern Scotia Sea, with a ≥40% decline in the mass of individual krill. Projections also suggest a 25% chance that krill biomass will fall below an established depletion threshold (75% of its unimpacted level), with consequent risks for some predator populations, especially penguins. Average penguin abundance declined by up to 30% of its unimpacted level, with up to a 50% chance of falling below the depletion threshold. Simulated krill fishing at currently permitted harvest rates further increased risks for depletion, and stopping fishing offset the increased risks associated with ocean warming in our model to some extent. These results varied by location and species group. Risk reductions at smaller spatial scales also differed from those at the regional level, which suggests that some predator populations may be more vulnerable than others to future changes in krill biomass. However, impacts on predators did not always map directly to those for krill. Our findings indicate the importance of identifying vulnerable marine populations and targeting protection measures at appropriate spatial scales, and the potential for spatially-structured management to avoid aggravating risks associated with rising ocean temperatures. This may help balance tradeoffs among marine ecosystem services in an uncertain future.

Tambora and the mackerel year: Phenology and fisheries during an extreme climate event.

Global warming has increased the frequency of extreme climate events, yet responses of biological and human communities are poorly understood, particularly for aquatic ecosystems and fisheries. Retrospective analysis of known outcomes may provide insights into the nature of adaptations and trajectory of subsequent conditions. We consider the 1815 eruption of the Indonesian volcano Tambora and its impact on Gulf of Maine (GoM) coastal and riparian fisheries in 1816. Applying complex adaptive systems theory with historical methods, we analyzed fish export data and contemporary climate records to disclose human and piscine responses to Tambora's extreme weather at different spatial and temporal scales while also considering sociopolitical influences. Results identified a tipping point in GoM fisheries induced by concatenating social and biological responses to extreme weather. Abnormal daily temperatures selectively affected targeted fish species-alewives, shad, herring, and mackerel-according to their migration and spawning phenologies and temperature tolerances. First to arrive, alewives suffered the worst. Crop failure and incipient famine intensified fishing pressure, especially in heavily settled regions where dams already compromised watersheds. Insufficient alewife runs led fishers to target mackerel, the next species appearing in abundance along the coast; thus, 1816 became the "mackerel year." Critically, the shift from riparian to marine fisheries persisted and expanded after temperatures moderated and alewives recovered. We conclude that contingent human adaptations to extraordinary weather permanently altered this complex system. Understanding how adaptive responses to extreme events can trigger unintended consequences may advance long-term planning for resilience in an uncertain future.