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At least 307 records · Page 17

Ultrafast laser filament-induced fluorescence for detecting uranium stress in Chlamydomonas reinhardtii

Abstract Plants and other photosynthetic organisms have been suggested as potential pervasive biosensors for nuclear nonproliferation monitoring. We demonstrate that ultrafast laser filament-induced fluorescence of chlorophyll in the green alga Chlamydomonas reinhardtii is a promising method for remote, in-field detection of stress from exposure to nuclear materials. This method holds an advantage over broad-area surveillance, such as solar-induced fluorescence monitoring, when targeting excitation of a specific plant would improve the detectability, for example when local biota density is low. After exposing C. reinhardtii to uranium, we find that the concentration of chlorophyll a, chlorophyll fluorescence lifetime, and carotenoid content increase. The increased fluorescence lifetime signifies a decrease in non-photochemical quenching. The simultaneous increase in carotenoid content implies oxidative stress, further confirmed by the production of radical oxygen species evidence in the steady-state absorption spectrum. This is potentially a unique signature of uranium, as previous work finds that heavy metal stress generally increases non-photochemical quenching. We identify the temporal profile of the chlorophyll fluorescence to be a distinguishing feature between uranium-exposed and unexposed algae. Discrimination of uranium-exposed samples is possible at a distance of $$\sim $$ ∼ 35 m with a single laser shot and a modest collection system, as determined through a combination of experiment and simulation of distance-scaled uncertainty in discriminating the temporal profiles. Illustrating the potential for remote detection, detection over 125 m would require 100 laser shots, commensurate with the detection time on the order of 1 s.

54 ENVIRONMENTAL SCIENCES↗

Genotypic analyses of IncHI2 plasmids from enteric bacteria

Incompatibility (Inc) HI2 plasmids are large (typically > 200 kb), transmissible plasmids that encode antimicrobial resistance (AMR), heavy metal resistance (HMR) and disinfectants/biocide resistance (DBR). To better understand the distribution and diversity of resistance-encoding genes among IncHI2 plasmids, computational approaches were used to evaluate resistance and transfer-associated genes among the plasmids. Complete IncHI2 plasmid (N - 667) sequences were extracted from GenBank and analyzed using AMRFinderPlus, IntegronFinder and Plasmid Transfer Factor database. The most common IncHI2-carrying genera included Enterobacter (N = 209), Escherichia (N = 208), and Salmonella (N = 204). Resistance genes distribution was diverse, with plasmids from Escherichia and Salmonella showing general similarity in comparison to Enterobacter and other taxa, which grouped together. Plasmids from Enterobacter and other taxa had a higher prevalence of multiple mercury resistance genes and arsenic resistance gene, arsC, compared to Escherichia and Salmonella. For sulfonamide resistance, sul1 was more common among Enterobacter and other taxa, compared to sul2 and sul3 for Escherichia and Salmonella. Similar gene diversity trends were also observed for tetracyclines, quinolones, β-lactams, and colistin. Over 99% of plasmids carried at least 25 IncHI2-associated conjugal transfer genes. These findings highlight the diversity and dissemination potential for resistance across different enteric bacteria and value of computational-based approaches for the resistance-gene assessment.

59 BASIC BIOLOGICAL SCIENCES↗

Exchange bias switching in an antiferromagnet/ferromagnet bilayer driven by spin-orbit torque

Here the electrical manipulation of magnetization and exchange bias in antiferromagnet/ferromagnet thin films could be of use in the development of the next generation of spintronic devices. Current-controlled magnetization switching can be driven by spin-orbit torques generated in an adjacent heavy metal layer, but these structures are difficult to integrate with exchange bias switching and tunnelling magnetoresistance measurements. Here, we report the current-induced switching of the exchange bias field in a perpendicularly magnetized IrMn/CoFeB bilayer structure using a spin-orbit torque generated in the antiferromagnetic IrMn layer. By manipulating the current direction and amplitude, independent and repeatable switching of the magnetization and exchange bias field below the blocking temperature can be achieved. The critical current density for the exchange bias switching is found to be larger than that for CoFeB magnetization reversal. X-ray magnetic circular dichroism, polarized neutron reflectometry measurements and micromagnetic simulations show that a small net magnetization within the IrMn interface plays a crucial role in these phenomena.

42 ENGINEERING↗

Prussian blue as a co-catalyst for enhanced Cr (VI) photocatalytic reduction promoted by titania-based nanoparticles and aerogels

Hexavalent chromium (Cr(VI)) is an noxious and highly toxic heavy metal that presents a serious threat to human health if present even in low concentrations in drinking water. Photocatalytic reduction of Cr(VI) to its less toxic Cr(III) state is a potential strategy to combat Cr(VI) pollution, but the efficiency of the process is low, especially in the absence of hole scavenger organic reagents. To address this issue and prepare efficient photocatalysts for Cr(VI) removal from water, in this study, we explored Prussian blue (PB) as a co-catalyst for improving the photoreduction performance of different high surface area TiO 2 -based materials (titania or silica–titania nanoparticles and aerogels). Here, the photocatalyst nanomaterials were surface-modified with nanocrystalline PB using the photodeposition route. The PB layer acts as an effective electron acceptor/mediator between the semiconductor photocatalyst and Cr(VI) species. All the PB-modified photocatalysts exhibit higher photocatalytic activity (up to 9 times faster) as compared to the unmodified photocatalysts towards reduction of Cr(VI). Importantly, the PB-modified photocatalysts exhibited high photocatalytic performance (98–99% reduction in 40 min for pH = 5.6 and in 10 min for pH = 3) without addition of organic reagents. The simple approach reported herein can be followed to prepare new PB-photocatalyst systems with improved photocatalytic performance towards Cr(VI) reduction and other target applications.

36 MATERIALS SCIENCE↗

Pressure-stimulus-responsive behaviors of core–shell InP/ZnSe nanocrystals: remarkable piezochromic luminescence and structural assembly

Piezochromic luminescence materials with optical properties can be adjusted (the colors most sensitive to the human eye range from red to green) to provide powerful means for information acquisition in various applications. Inorganic quantum dots, typically based on heavy metals such as cadmium and lead, have congenital advantages as luminescence materials, including strong inoxidizability and excellent photoelectric properties. However, small band-gap shifts under pressure have hindered the development of inorganic-based piezochromic materials. In this study, we combined in situ high-pressure photoluminescence (PL) and absorption measurements with synchrotron X-ray scattering spectra to elucidate the remarkable modulation of optical properties and morphologies by pressure, particularly that of the piezochromic luminescence, in all-inorganic core–shell InP/ZnSe nanocrystals (NCs). We observed a stepwise PL color change from red to green, and an ultrabroad bandgap tunability of 0.46 eV was observed from 1.99 to 2.45 eV in the pressure range of 14.2 GPa for InP/ZnSe NCs. Moreover, two-dimensional (2D) InP/ZnSe nanosheets were synthesized by the stress-driven attachment of nanoparticles. These results demonstrate the ability of the pressure-stimulus response to trigger remarkable piezochromic luminescence and 2D nanosheet assembly in InP/ZnSe NCs, which paves the way for new applications of all-inorganic InP-based semiconductor NCs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Back in bismuth: controlling triplet energy transfer, phosphorescence, and radioluminescence via supramolecular interactions

Five bismuth(III)-organic phases that consist of supramolecular assemblies of Bi-2,6-pyridinedicarboxylate structural units and substituted 1,10-phenanthroline molecules (R-Phen; R = H, 5-methyl, 5-chloro, 2,9-dimethyl, and 2,9-dicholoro) were synthesized. All five compounds exhibited solid-state photoluminescence. Whereas the phases containing 2,9-dimethylphenanthroline (Me 2 Phen) and 2,9-dichlorophenanthroline (Cl 2 Phen) displayed solely phosphorescence, the structures built from 5-methylphenanthroline and 5-chlorophenanthroline showed exclusively fluorescence. The remaining phase, consisting of phenanthrolinium, exhibited both fluorescence and phosphoresence. It was determined that phosphorescence arises from triplet state emission (T 1 → S 0 ) of substituted R-Phen units while fluorescence originates from Bi(III) coordinated pyrdinedicarboxylate ligands. Bismuth induces spin–orbit coupling for triplet state population and additionally acts as a heavy metal attenuator for X-ray luminescence (radioluminescence). The electronic structure was mapped and excitation pathway investigated via density functional theory calculations. Computational findings indicate favorable conditions for triplet energy transfer from donor Bi(III)-organic units to acceptor R-Phen derivatives. It is proposed that for the phosphorescent compounds, strong π–π interactions promote electron transfer, whereas the compounds that exhibit purely fluorescence lack any such π–π interactions and undergo triplet energy transfer. In conclusion, these results provide a useful platform for probing structure–property relationships of luminescent bismuth-organic compounds, and specifically highlights the role of noncovalent interactions in achieving room temperature phosphorescence and radioluminescence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Systematic characterization of selenium speciation in coal fly ash

Millions of tons of coal fly ashes (CFAs) are produced annually during coal combustion in the U.S., which are commonly beneficially used in the concrete industry or disposed of in ash ponds. CFAs contain trace amounts of a range of toxic heavy metals including selenium (Se). Because the toxicity of Se is dependent on its speciation, investigating Se speciation in CFAs as affected by coal source and combustion conditions can help understand the related environmental and human health impacts during disposal or beneficial reuse. In this study, a set of representative CFA samples were characterized for Se speciation using synchrotron X-ray absorption spectroscopy (XAS) and micro-X-ray fluorescence spectromicroscopy (μ-XRF/XAS). Se-containing particles were highly heterogeneous, and individual particles might contain multiple oxidation states including Se(0), Se(IV), and Se(VI). Principal component analysis was performed for sample characteristics including Al 2 O 3 , SiO 2 , CaO, FeO, loss on ignition, average particle size, Se concentration, and Se oxidation state. Selective catalytic reduction (SCR), which is used to limit nitrogen oxide (NO x ) emissions during coal combustion, was found to be associated with the presence of reduced Se oxidation states, with up to 90% Se(0) observed in samples with SCR. Alongside SCR, FeO content may also influence Se speciation.

01 COAL, LIGNITE, AND PEAT↗

Structure and function of aerotolerant, multiple-turnover THI4 thiazole synthases

Plant and fungal THI4 thiazole synthases produce the thiamin thiazole moiety in aerobic conditions via a single-turnover suicide reaction that uses an active-site Cys residue as sulfur donor. Multiple-turnover (i.e. catalytic) THI4s lacking an active-site Cys (non-Cys THI4s) that use sulfide as sulfur donor have been biochemically characterized -- but only from archaeal methanogens that are anaerobic, O 2 -sensitive hyperthermophiles from sulfide-rich habitats. These THI4s prefer iron as cofactor. A survey of prokaryote genomes uncovered non-Cys THI4s in aerobic mesophiles from sulfide-poor habitats, suggesting that multiple-turnover THI4 operation is possible in aerobic, mild, low-sulfide conditions. This was confirmed by testing 23 representative non-Cys THI4s for complementation of an Escherichia coli ΔthiG thiazole auxotroph in aerobic conditions. Sixteen were clearly active, and more so when intracellular sulfide level was raised by supplying Cys, demonstrating catalytic function in the presence of O 2 at mild temperatures and indicating use of sulfide or a sulfide metabolite as sulfur donor. Comparative genomic evidence linked non-Cys THI4s with proteins from families that bind, transport, or metabolize cobalt or other heavy metals. The crystal structure of the aerotolerant bacterial Thermovibrio ammonificans THI4 was determined to probe the molecular basis of aerotolerance. The structure suggested no large deviations compared with the structures of THI4s from O 2 -sensitive methanogens, but is consistent with an alternative catalytic metal. Together with complementation data, use of cobalt rather than iron was supported. We conclude that catalytic THI4s can indeed operate aerobically and that the metal cofactor inserted is a likely natural determinant of aerotolerance.

59 BASIC BIOLOGICAL SCIENCES↗

Observation of spatially resolved Rashba states on the surface of CH 3 NH 3 PbBr 3 single crystals

Hybrid organic-inorganic perovskites (HOIPs) are prime candidates for studying Rashba effects due to the heavy metal and halogen atoms in their crystal structure coupled with predicted inversion symmetry breaking. Nevertheless, observation of the Rashba effect in cubic CH 3 NH 3 PbBr 3 single crystals that possess bulk inversion symmetry is the subject of extensive debate due to the lack of conclusive experiments and theoretical explanations. In this work, we provide experimental evidence that Rashba state in cubic CH 3 NH 3 PbBr 3 single crystals at room temperature occurs exclusively on the crystal surface and depends on specific surface termination that results in local symmetry breaking. We demonstrate this using a suite of spatially resolved and depth-sensitive techniques, including circular photogalvanic effect, inverse spin Hall effect, and multiphoton microscopy, that are supported by first principle calculations. Our work suggests using surface Rashba states in these materials for spintronic applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Mechanisms of shape transfer and preheating in indirect-drive double shell collisions

Implosions of Hohlraum-driven double shell targets as an alternative inertial confinement fusion concept are underway at the National Ignition Facility. The double shell system relies on a series of energy transfer processes starting from thermal x-ray absorption by the outer shell, followed by collisional transfer of kinetic energy to a heavy metal inner shell, and finally, conversion to the internal energy of the deuterium-tritium fuel. During each of these energy transfer stages, low-mode asymmetries can act to reduce the ideal transfer efficiency degrading double shell performance. Mechanisms, such as hard x-ray preheat from the Hohlraum, not only decrease the efficiency of kinetic energy transfer but may also be a source of low-mode asymmetry. In this article, we evaluate the shape transfer processes through the time of shell collision using two-dimensional integrated Hohlraum and capsule computations. We find that the dominant mode of the shape transfer is well described using a “radial impulse” model from the shape of the foam pressure reservoir. To evaluate the importance of preheat on inner shell shape, we also report on first measurements of Au L-shell preheat asymmetry in a double shell with a tungsten pusher. These measurements showed a 65% higher preheat velocity at the pole of the capsule relative to the equator. We also found that the experiments provided rigorous constraints by which to test the Hohlraum model settings that impact the amount and symmetry of Au L-shell preheat via the plasma conditions inside the outer cone Au bubble.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Reactive co-sputtering of ternary Au–Ta–O films with tunable electrical resistivity

Heavy-metal-based films with high electrical resistivity are needed for hohlraums for magnetically-assisted inertial confinement fusion. Here, we study ternary Au-Ta-O films deposited by reactive direct-current magnetron co-sputtering from elemental Au and Ta targets in an oxygen containing atmosphere. By varying O content, the electrical resistivity of films can be tuned in a wide range of ~ 100 - 40,000 μΩ cm. With increasing O content, a drastic increase in resistivity occurs at ~ 45 at.% of O, separating regimes with two different dominant conduction mechanisms attributed to metallic conduction through the Au-Ta alloy matrix (for ≲ 45 at.% of O) and tunneling across insulating Ta 2 O 5 layers separating conducting islands (for ≳ 45 at.% of O). Post-deposition annealing at 300 °C leads to the segregation of Au into ~ 50-nm islands, sharply decreasing the resistivity for films with ≳ 45 at.% of O but not for the metal-like films with lower O content.

36 MATERIALS SCIENCE↗

Boron coordination change in barium borate melts and glasses and its contribution to configurational heat capacity, entropy, and fragility

High-energy x-ray diffraction from molten and glassy BaB 2 O 4 and BaB 4 O 7 has been performed using aerodynamic levitation and laser heating over a wide range of temperatures. Remarkably, even in the presence of a heavy metal modifier dominating x-ray scattering, it was possible to extract accurate values for the tetrahedral, sp 3 , boron fraction, N 4 , which declines with increasing temperature, using bond valence-based mapping from the measured mean B–O bond lengths while accounting for vibrational thermal expansion. These are used within a boron-coordination-change model to extract enthalpies, ΔH, and entropies, ΔS, of isomerization between sp 2 and sp 3 boron. The results for BaB 4 O 7 , ΔH = 22(3) kJ mol -1 boron, ΔS = 19(2) J mol -1 boron K -1 , agree quantitatively with those found previously for Na 2 B 4 O 7 . Analytical expressions for N 4 (J, T) and associated configurational heat capacity, $C_{P}^{conf}$(J, T), and entropy, S conf (J, T), contributions are extended to cover a wide composition range 0 ≤ J = BaO/B 2 O 3 ≤ 3 using a model for ΔH(J) and ΔS(J) derived empirically for lithium borates. Maxima in the $C_{P}^{conf}$(J, T g ) and fragility index contributions are thereby predicted for J ≲ 1, higher than the maximum observed and predicted in N 4 (J, T g ) at J ≃ 0.6. We discuss the utility of the boron-coordination-change isomerization model in the context of borate liquids containing other modifiers and the prospect of neutron diffraction to aid in empirical determinations of modifier-dependent effects, illustrated by new neutron diffraction data on Ba 11 B 4 O 7 glass, its well-known α-polymorph, and lesser-known δ-phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of magnetic anisotropy in the magnetoresistance of Cr 2 O 3 /Al 2 O 3 thin film antiferromagnets

The magnetic states of antiferromagnetic insulating thin films are a promising medium for information storage, but characterization of these states has proven to be challenging. One approach is via magnetotransport measurements in an adjacent heavy metal layer. To this end, we synthesized and characterized a series of Cr 2 O 3 films and bilayers on Al 2 O 3 substrates with three different orientations: m-plane, a-plane, and c-plane. X-ray diffraction results demonstrated orientation control of the Cr 2 O 3 thin film, with m-plane films displaying a higher degree of mosaic spread than the a- and c-plane films. Reciprocal space maps showed that the films are mostly relaxed, although there was a small and different degree of strain in each orientation. The m-plane films were under 2% compressive strain, the a-plane film was under 0.5% compressive strain, and the c-plane film was completely relaxed to bulk values. To probe the magnetic state of the films, we measured the angular dependent magnetoresistance of Cr 2 O 3 /Pt bilayers for each orientation. We found a nontrivial temperature dependence of the sign of the magnetoresistance, pointing to the complex interplay between the exchange and anisotropy energies that vary with orientation. We propose that strain and mosaic spread may contribute to a difference in magnetic anisotropies among the samples and the resulting temperature dependence of the magnetoresistance. This work demonstrates the importance of considering the competition between antiferromagnetic exchange and magnetic anisotropy when storing information in the spin state of an antiferromagnetic insulator.

42 ENGINEERING↗

A structural framework for unidirectional transport by a bacterial ABC exporter

The ATP-binding cassette (ABC) transporter of mitochondria (Atm1) mediates iron homeostasis in eukaryotes, while the prokaryotic homolog from Novosphingobium aromaticivorans (NaAtm1) can export glutathione derivatives and confer protection against heavy-metal toxicity. To establish the structural framework underlying the NaAtm1 transport mechanism, we determined eight structures by X-ray crystallography and single-particle cryo-electron microscopy in distinct conformational states, stabilized by individual disulfide crosslinks and nucleotides. As NaAtm1 progresses through the transport cycle, conformational changes in transmembrane helix 6 (TM6) alter the glutathione-binding site and the associated substrate-binding cavity. Significantly, kinking of TM6 in the post-ATP hydrolysis state stabilized by MgADPVO4 eliminates this cavity, precluding uptake of glutathione derivatives. The presence of this cavity during the transition from the inward-facing to outward-facing conformational states, and its absence in the reverse direction, thereby provide an elegant and conceptually simple mechanism for enforcing the export directionality of transport by NaAtm1. One of the disulfide crosslinked NaAtm1 variants characterized in this work retains significant glutathione transport activity, suggesting that ATP hydrolysis and substrate transport by Atm1 may involve a limited set of conformational states with minimal separation of the nucleotide-binding domains in the inward-facing conformation.

59 BASIC BIOLOGICAL SCIENCES↗

Genome-wide toxicogenomic study of the lanthanides sheds light on the selective toxicity mechanisms associated with critical materials

Significance The growing use of lanthanides in various industries has increased the potential for human exposure to large concentrations of these heavy metals throughout the life cycle of new technologies, requiring more detailed investigations into their toxicological properties. The eukaryote model organism Saccharomyces cerevisiae is ideal to apply functional toxicogenomics tools at the system level and probe fundamental cellular functions disrupted by rare-earth metals. A comprehensive mechanistic assay was conducted to evaluate toxicity across the entire lanthanide series and provide information about which toxicological mechanisms may be shared by the different metals. We identified distinct characteristic behaviors between early and middle/late lanthanides, highlighting the powerful discrimination capabilities of natural systems and pointing to detailed mechanistic pathways associated with lanthanide exposure.

59 BASIC BIOLOGICAL SCIENCES↗

Chirality enhances oxygen reduction

Controlled reduction of oxygen is important for developing clean energy technologies, such as fuel cells, and is vital to the existence of aerobic organisms. The process starts with oxygen in a triplet ground state and ends with products that are all in singlet states. Hence, spin constraints in the oxygen reduction must be considered. Here, we show that the electron transfer efficiency from chiral electrodes to oxygen (oxygen reduction reaction) is enhanced over that from achiral electrodes. We demonstrate lower overpotentials and higher current densities for chiral catalysts versus achiral ones. This finding holds even for electrodes composed of heavy metals with large spin–orbit coupling. The effect results from the spin selectivity conferred on the electron current by the chiral assemblies, the chiral-induced spin selectivity effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular surface programming of rectifying junctions between InAs colloidal quantum dot solids

Heavy-metal-free III–V colloidal quantum dots (CQDs) show promise in optoelectronics: Recent advancements in the synthesis of large-diameter indium arsenide (InAs) CQDs provide access to short-wave infrared (IR) wavelengths for three-dimensional ranging and imaging. In early studies, however, we were unable to achieve a rectifying photodiode using CQDs and molybdenum oxide/polymer hole transport layers, as the shallow valence bandedge (5.0 eV) was misaligned with the ionization potentials of the widely used transport layers. This occurred when increasing CQD diameter to decrease the bandgap below 1.1 eV. Here, we develop a rectifying junction among InAs CQD layers, where we use molecular surface modifiers to tune the energy levels of InAs CQDs electrostatically. Previously developed bifunctional dithiol ligands, established for II-VI and IV-VI CQDs, exhibit slow reaction kinetics with III-V surfaces, causing the exchange to fail. Here, we study carboxylate and thiolate binding groups, united with electron-donating free end groups, that shift upward the valence bandedge of InAs CQDs, producing valence band energies as shallow as 4.8 eV. Photophysical studies combined with density functional theory show that carboxylate-based passivants participate in strong bidentate bridging with both In and As on the CQD surface. The tuned CQD layer incorporated into a photodiode structure achieves improved performance with EQE (external quantum efficiency) of 35% (>1 μm) and dark current density < 400 nA cm -2 , a >25% increase in EQE and >90% reduced dark current density compared to the reference device. This work represents an advance over previous III-V CQD short-wavelength IR photodetectors (EQE < 5%, dark current > 10,000 nA cm -2 ).

36 MATERIALS SCIENCE↗

S-adenosyl-L-methionine is the unexpected methyl donor for the methylation of mercury by the membrane-associated HgcAB complex

Mercury (Hg) is a heavy metal that exhibits high biological toxicity. Monomethylmercury and dimethylmercury are neurotoxins and a significant environmental concern as they bioaccumulate and biomagnify within the aquatic food web. Microbial Hg methylation involves two proteins, HgcA and HgcB. Here, we show that HgcA and HgcB can be heterologously coexpressed, and the HgcAB complex can be purified. We demonstrated that HgcA is a membrane-associated cobalamin-dependent methyltransferase and HgcB is a ferredoxin-like protein containing two [4Fe-4S] clusters. Further, spectroscopic and kinetic results demonstrate that S-adenosyl-L-methionine (SAM) donates the methyl group to Hg in a two-step reaction involving a methylcob(III)alamin intermediate including Co-thiolate ligation from a conserved Cys residue. Our findings uncover a biological role for SAM in microbial Hg methylation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗