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At least 145 records · Page 8

Microbial Diffraction Gratings as Optical Detectors for Heavy Metal Pollutants

As a significant industrial pollutant, cadmium is implicated as the cause of itai-itai disease. For biological detection of cadmium toxicity, an assay device has been developed using the motile response of the protozoa species, Tetrahymena pyriformis. This mobile protozoa measures 50 microns in diameter, swims at 10 body lengths per second, and aggregates into macroscopically visible patterns at high organism concentrations. The assay demonstrates a Cd(+2) sensitivity better than 1 micro-M and a toxicity threshold to 5 micro-M, thus encouraging the study of these microbial cultures as viable pollution detectors. Using two-dimensional diffraction patterns within a Tetrahymena culture, the scattered light intensity varies with different organism densities (population counts). The resulting density profile correlates strongly with the toxic effects at very low dosages for cadmium (less than 5 ppm) and then for poison protection directly (with nickel and copper antagonists competing with cadmium absorption). In particular, copper dosages as low as 0.1-0.5 mM Cu have shown protective antagonism against cadmium, have enhanced density variability for cultures containing 1 mM Cd(+2) and therefore have demonstrated the sensitivity of the optical detection system. In this way, such microbial diffraction patterns give a responsive optical measure of biological culture changes and toxicity determination in aqueous samples of heavy metals and industrial pollutants.

Noever, David↗

Engineering the Interlayer Spacing by Pre-Intercalation for High Performance Supercapacitor MXene Electrodes in Room Temperature Ionic Liquid

MXenes exhibit excellent capacitance at high scan rates in sulfuric acid aqueous electrolytes, but the narrow potential window of aqueous electrolytes limits the energy density. Organic electrolytes and room-temperature ionic liquids (RTILs) can provide higher potential windows, leading to higher energy density. The large cation size of RTIL hinders its intercalation in-between the layers of MXene limiting the specific capacitance in comparison to aqueous electrolytes. In this work, different chain lengths alkylammonium (AA) cations are intercalated into Ti 3 C 2 T x , producing variation of MXene interlayer spacings (d-spacing). AA-cation-intercalated Ti 3 C 2 T x (AA-Ti 3 C 2 ), exhibits higher specific capacitances, and cycling stabilities than pristine Ti 3 C 2 T x in 1 m 1-ethly-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide (EMIMTFSI) in acetonitrile and neat EMIMTFSI RTIL electrolytes. Pre-intercalated MXene with an interlayer spacing of ≈2.2 nm, can deliver a large specific capacitance of 257 F g –1 (1428 mF cm –2 and 492 F cm –3 ) in neat EMIMTFSI electrolyte leading to high energy density. Quasi elastic neutron scattering and electrochemical impedance spectroscopy are used to study the dynamics of confined RTIL in pre-intercalated MXene. Furthermore, molecular dynamics simulations suggest significant differences in the structures of RTIL ions and AA cations inside the Ti 3 C 2 T x interlayer, providing insights into the differences in the observed electrochemical behavior.

36 MATERIALS SCIENCE↗

Measurements of the imploding plasma sheath in triple-nozzle gas-puff z pinches

Gas-puff z-pinch implosions are characterized by the formation of a dense annular plasma shell, the sheath, that is driven to the axis by magnetic forces and therefore subject to the magneto-Rayleigh–Taylor instability. Here, the conditions within these sheaths are measured on the 1-MA COBRA generator at Cornell University for various gas species and initial fill densities. The gas-puff loads are initialized by a 7 cm diameter triple-nozzle gas valve assembly with concentric outer and inner annular nozzles and a central gas jet. Thomson scattering and laser interferometry provide spatially resolved flow, temperature, and electron density profiles midway through the implosion, while extreme ultraviolet pinhole cameras record the evolution of the plasma column and photoconducting diodes measure x-ray emission. Analysis of the scattering spectra includes a means of discriminating between thermal and non-thermal broadening to test for the presence of hydrodynamic turbulence. Two types of sheath profiles are observed, those with sharp discontinuities at the leading edge and those with smooth gradients. In both cases, non-thermal broadening is generally peaked at the front of the sheath and exhibits a characteristic decay length that roughly scales with the sheath ion mean free path. Here, we demonstrate that this non-thermal broadening term is inconsistent with laminar velocity gradients and is more consistent with dissipative turbulence driven by unstable plasma waves in a collisionless shock. The resulting differences in sheath profile are then set by the sheath ion collisionality in a manner consistent with recent 1D kinetic simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Confinement of many-body Bethe strings

Based on the Bethe ansatz approach and inelastic neutron scattering experiments, we reveal the evolution of confinement of many-body Bethe strings in ordered regions of the quasi-one-dimensional antiferromagnet YbAlO 3 . In the antiferromagnetic phase, the spin dynamics is dominated by confined length-1 Bethe strings, whose dominancy in the high-energy branch of the excitation spectrum yields to confined length-2 Bethe strings when the material is tuned to the spin-density-wave phase. In the thermal-induced disordered region, the confinement effect disappears, and the system restores the conventional quantum integrable physics of the one-dimensional Heisenberg model. Finally, our results establish a unified picture based on a Bethe string for the spin dynamics in different magnetic phases of YbAlO 3 , and thus provide profound insight into many-body quantum magnetism.

1-dimensional spin chains↗

Genetic Fusion of Thermoresponsive Polypeptides with UCST‐type Behavior Mediates 1D Assembly of Coiled‐Coil Bundlemers

Abstract Thermoresponsive resilin‐like polypeptides (RLPs) of various lengths were genetically fused to two different computationally designed coiled coil‐forming peptides with distinct thermal stability, to develop new strategies to assemble coiled coil peptides via temperature‐triggered phase separation of the RLP units. Their successful production in bacterial expression hosts was verified via gel electrophoresis, mass spectrometry, and amino acid analysis. Circular dichroism (CD) spectroscopy, ultraviolet‐visible (UV/Vis) turbidimetry, and dynamic light scattering (DLS) measurements confirmed the stability of the coiled coils and showed that the thermosensitive phase behavior of the RLPs was preserved in the genetically fused hybrid polypeptides. Cryogenic‐transmission electron microscopy and coarse‐grained modeling revealed that functionalizing the coiled coils with thermoresponsive RLPs leads to their thermally triggered noncovalent assembly into nanofibrillar assemblies.

Patkar, Sai S.↗

Confined magnons

Magnetic structures are known to possess magnon excitations confined to their surfaces and interfaces, but these spatially localized modes are often not resolved in spectroscopy experiments. In this work, we develop a theory to calculate the confined magnon spectra and its associated spin scattering function, which is the physical observable in neutron and electron scattering, and a proxy for photon spectroscopy based on x-ray, Raman, and terahertz (THz) sources. We show that extra anisotropy at the surface or interface plays a key role in magnon confinement. We obtain analytical expressions for the confinement length scale and show that it is qualitatively similar for ferromagnets and antiferromagnets in dimension d≥2. For d=1, we find remarkable differences between ferromagnetic and antiferromagnetic models. The theory indicates the presence of several confined magnon resonances in addition to the usual magnons thought to explain the excitations of magnetic nanostructures. Detecting these modes may elucidate the impact of the interface on spin anisotropy and magnetic order.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Evaluation of current tropospheric mapping functions by Deep Space Network very long baseline interferometry

To compare the validity of current algorithms that map zenith tropospheric delay to arbitrary elevation angles, 10 different tropospheric mapping functions are used to analyze the current data base of Deep Space Network Mark 3 intercontinental very long baseline interferometric (VLBI) data. This analysis serves as a stringent test because of the high proportion of low-elevation observations necessitated by the extremely long baselines. Postfit delay and delay-rate residuals are examined, as well as the scatter of baseline lengths about the time-linear model that characterizes tectonic motion. Among the functions that utilize surface meteorological data as input parameters, the Lanyi 1984 mapping shows the best performance both for residuals and baselines, through the 1985 Davis function is statistically nearly identical. The next best performance is shown by the recent function of Niell, which is based on an examination of global atmospheric characteristics as a function of season and uses no weather data at the time of the measurements. The Niell function shows a slight improvement in residuals relative to Lanyi, but also an increase in baseline scatter that is significant for the California-Spain baseline. Two variants of the Chao mapping function, as well as the Chao tables used with the interpolation algorithm employed in the Orbit Determination Program software, show substandard behavior for both VLBI residuals and baseline scatter. The length of the California-Australia baseline (10,600 km) in the VLBI solution can vary by as much as 5 to 10 cm for the 10 mapping functions.

Sovers, O. J.↗

Dispersion of high oxygen permeability ionomers in water-propanol solutions

There is a growing interest in high oxygen permeability ionomers (HOPI) for better-performing proton exchange membrane fuel cell (PEMFC) catalyst layers. In this study, we used small-angle x-ray scattering (SAXS) to analyze dispersions of two types of perfluorinated sulfonic acid (PFSA) ionomers and a HOPI in water and propanol solvents, at concentrations between 1 wt% and 15 wt%. HOPI dispersions exhibited the interference peak typical of ionomers; by separately fitting the peak and higher- q regions with several models, we demonstrated that HOPI aggregates have a closer average spacing than conventional PFSA ionomers, and smaller aggregate size when assuming a cylindrical geometry. By measuring conventional PFSA ionomers with two side chain lengths and several equivalent weights, we showed that these side chain parameters alone did not explain the differences in aggregate spacing or size. In addition, the pattern was present whether samples were prepared in a 50/50 water/propanol or a more propanol-rich mixture. As such, the structural differences of HOPI could be due to its different backbone monomer. A better understanding of the influence of the HOPI chemistry on dispersion properties could help explain the ink structure and drying characteristics of HOPI observed in prior work. Future study of ionomer-catalyst mixtures, such as measuring ionomer adsorption to carbon, would help elucidate the role of ionomer from ink formulation to the cast electrode.

Aquivion↗

Ink-substrate interactions during 3D printing revealed by time-resolved coherent X-ray scattering

Additive printing techniques are regarded as revolutionary and versatile methods of advanced device manufacturing, stemming from the possibility to pattern materials on a custom-based approach and the potential to create novel microstructures and achieve new functionalities. Despite these advantages, the inherent anisotropy of the printing process is a source of property gradients within the printed materials, often associated with variable and/or poor performance. Up to date, the evolutionary pathways associated with printing have largely remained unaddressed, mainly owing to the difficulty to study the transformations induced in the material during processing. Time-resolved coherent X-ray scattering techniques, such as X-ray photon correlation spectroscopy, enable the in situ study of transient nanoscale and mesoscale states in a large variety of materials, including amorphous ones, by directly accessing the most relevant timescales and length scales of their nanoscale and mesoscale dynamics, self-assembly, and mesostructure evolution. In this work, we conduct in operando studies of continuous-flow direct writing with colloidal inks, focusing on how the ink formulation and ink-substrate interactions affect the processes that determine the macroscopic properties of the printed materials. We find fundamental differences in the ink structural relaxations emerging from the primary colloid properties (monodisperse versus aggregated colloids) and the substrates surface energy and mechanical properties. Our work helps to reveal and quantify the basic science governing the evolution of 3D-printed materials during processing, ultimately improving engineering criteria for the design of printable materials.

36 MATERIALS SCIENCE↗

Hierarchical Self-Assembly of Carbon Dots into High-Aspect-Ratio Nanowires

Here, we report a spontaneous and hierarchical self-assembly mechanism of carbon dots prepared from citric acid and urea into nanowire structures with large aspect ratios (>50). Scattering-type scanning near-field optical microscopy (s-SNOM) with broadly tunable mid-IR excitation was used to interrogate details of the self-assembly process by generating nanoscopic chemical maps of local wire morphology and composition. s-SNOM images capture the evolution of wire formation and the complex interplay between different chemical constituents directing assembly over the nano- to microscopic length scales. We propose that residual citrate promotes tautomerization of melamine surface functionalities to produce supramolecular shape synthons comprised of melamine-cyanurate adducts capable of forming long-range and highly directional hydrogen-bonding networks. This intrinsic, heterogeneity-driven self-assembly mechanism reflects synergistic combinations of high chemical specificity and long-range cooperativity that may be harnessed to reproducibly fabricate functional structures on arbitrary surfaces.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Analytical optical scattering in clouds

An analytical optical model for scattering of light due to lightning by clouds of different geometry is being developed. The self-consistent approach and the equivalent medium concept of Twersky was used to treat the case corresponding to outside illumination. Thus, the resulting multiple scattering problem is transformed with the knowledge of the bulk parameters, into scattering by a single obstacle in isolation. Based on the size parameter of a typical water droplet as compared to the incident wave length, the problem for the single scatterer equivalent to the distribution of cloud particles can be solved either by Mie or Rayleigh scattering theory. The super computing code of Wiscombe can be used immediately to produce results that can be compared to the Monte Carlo computer simulation for outside incidence. A fairly reasonable inverse approach using the solution of the outside illumination case was proposed to model analytically the situation for point sources located inside the thick optical cloud. Its mathematical details are still being investigated. When finished, it will provide scientists an enhanced capability to study more realistic clouds. For testing purposes, the direct approach to the inside illumination of clouds by lightning is under consideration. Presently, an analytical solution for the cubic cloud will soon be obtained. For cylindrical or spherical clouds, preliminary results are needed for scattering by bounded obstacles above or below a penetrable surface interface.

Phanord, Dieudonne D.↗

Mapping the Morphology of DNA on Carbon Nanotubes in Solution Using X-ray Scattering Interferometry

Single-walled carbon nanotubes (SWCNTs) with adsorbed single-stranded DNA (ssDNA) are applied as sensors to investigate biological systems, with potential applications ranging from clinical diagnostics to agricultural biotechnology. Unique ssDNA sequences render SWCNTs selectively responsive to target analytes such as (GT)n-SWCNTs recognizing the neuromodulator, dopamine. It remains unclear how the ssDNA conformation on the SWCNT surface contributes to functionality, as observations have been limited to computational models or experiments under dehydrated conditions that differ substantially from the aqueous biological environments in which the nanosensors are applied. We demonstrate a direct mode of measuring in-solution ssDNA geometries on SWCNTs via X-ray scattering interferometry (XSI), which leverages the interference pattern produced by AuNP tags conjugated to ssDNA on the SWCNT surface. We employ XSI to quantify distinct surface-adsorbed morphologies for two (GT) n ssDNA oligomer lengths (n = 6, 15) that are used on SWCNTs in the context of dopamine sensing and measure the ssDNA conformational changes as a function of ionic strength and during dopamine interaction. Here, we show that the shorter oligomer, (GT) 6 , adopts a more periodically ordered ring structure along the SWCNT axis (inter-ssDNA distance of 8.6 ± 0.3 nm), compared to the longer (GT) 15 oligomer (most probable 5'-to-5' distance of 14.3 ± 1.1 nm). During molecular recognition, XSI reveals that dopamine elicits simultaneous axial elongation and radial constriction of adsorbed ssDNA on the SWCNT surface. Our approach using XSI to probe solution-phase morphologies of polymer-functionalized SWCNTs can be applied to yield insights into sensing mechanisms and inform future design strategies for nanoparticle-based sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

$J/\psi $-p scattering length from the total and differential photoproduction cross sections

The J/ψ-p scattering length, αJ/ψp, can be extracted from the J/ψ photoproduction cross section near threshold using the Vector Meson Dominance (VMD) model to relate the reaction γp→J/ψp to J/ψp→J/ψp. Such estimates based on experimental data result in values for |αJ/ψp|, which are much lower than most of the theoretical predictions. In this work, we study the relations between the different results, depending on the use of the total or the differential cross sections, and the method of extrapolating the data to threshold in the case of a low-statistics data sample, such as the near threshold J/ψ photoproduction dataset. We estimate a range for |αJ/ψp| of 0.003–0.025 fm as extracted from experimental data within the VMD model and discuss possible reasons for such lower values compared to the theoretical results.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Overview of Biomineralization and Nanobacteria

Biomineralization is a frequently used term in nanotechnology, astrobiology, geology, and medicine. In the process of biomineralization, a living organism provides a chemical environment that controls the nucleation and growth of unique mineral phases. Often these materials exhibit hierarchical structural order, leading to superior physical properties, not found either in their inorganic counterparts or in synthetic materials. Biomineralization is widespread in the biosphere and hundreds of different minerals are produced or assisted by a variety of organisms from bacteria to humans. Teeth, bones, kidney stones, and skeletons of algae, mussels, and magnetotactic bacteria are all examples of biomineralization. We do not fully understand the control mechanism of biomineralization either in primitive or in developed organisms. The presence of organic molecules, among other characteristics, can influence the coherence length for X-ray scattering in biogenic crystals. Control over biomineral properties can be accomplished at a myriad of levels, including the regulation of particle size, shape, crystal orientation, polymorphic structure, defect texture, and particle assembly. In the latter case, cellular processes enable control in both the spatial and temporal domain in such a way that hierarchical composite structures can be built which increase the toughness and durability of the material, which is invaluable for load-bearing materials such as bones, teeth, mollusk shells, etc. Durability of biominerals produces remarkably preserved bacterial and cyanobacterial microfossils from billions of years-old samples. The differentiation between microfossils and nonbiogenic artifacts has been a lively discussion subject in astrobiology especially in the last decade. Clearly, more detailed information on the mechanism of biomineralization, and the effect of organic matter on crystal formation/fossilization would help focus such discussions.

Ciftcioglu, N.↗

Wave direction measured by four different systems

A March 1977 wave direction measurement experiment is reported in which four systems were used to provide offshore wave-direction information: (1) synthetic aperture radar (SAR), (2) a coastal imaging radar, (3) an offshore pressure-gage array, and (4) aerial photography. From the coastal radar images and aerial photographs, the direction and length of the principal wavetrains were measured by a manual analysis. The SAR images were processed using fast Fourier transform to give two-dimensional wave spectra. Scatter diagrams are presented which intercompare the measurements of all four systems, and show good agreement among all imaging systems. It is concluded that aerial photography and SAR will prove more useful when wave measurements are needed over a large area or when there are rapidly changing wave characteristics.

Mattie, M. G.↗

Physics-Informed Generative Adversarial Networks for Stochastic Differential Equations

We developed a new class of physics-informed generative adversarial networks (PI-GANs) to solve forward, inverse, and mixed stochastic problems in a unified manner based on a limited number of scattered measurements. Unlike standard GANs relying solely on data for training, here we encoded into the architecture of GANs the governing physical laws in the form of stochastic differential equations (SDEs) using automatic differentiation. In particular, we applied Wasserstein GANs with gradient penalty (WGAN-GP) for its enhanced stability compared to vanilla GANs. We first tested WGAN-GP in approximating Gaussian processes of different correlation lengths based on data realizations collected from simultaneous reads at sparsely placed sensors. We obtained good approximation of the generated stochastic processes to the target ones even if there is a mismatch between the input noise dimensionality and the effective dimensionality of the target stochastic processes. We also studied the overfitting issue for both the discriminator and the generator, and we found that overfitting occurs also in the generator in addition to the discriminator as previously reported. Subsequently, we considered the solution of elliptic SDEs requiring approximations of three stochastic processes, namely the solution, the forcing, and the diffusion coefficient. Here again, we assumed data collected from simultaneous reads at a limited number of sensors for the multiple stochastic processes. Furthermore, three generators were used for the PI-GANs: two of them were feed forward deep neural networks (DNNs), while the other one was the neural network induced by the SDE. For the case where we have one group of data, we employed one feed forward DNN as the discriminator, while for the case of multiple groups of data we employed multiple discriminators in PI-GANs. We solved forward, inverse, and mixed problems without changing the framework of PI-GANs, obtaining both the means and the standard deviations of the stochastic solution and the diffusion coefficient in good agreement with benchmarks. In this work, we have demonstrated the effectiveness of PI-GANs in solving SDEs for about 120 dimensions. In principle, PI-GANs could tackle very high dimensional problems given more sensor data with low-polynomial growth in computational cost.

97 MATHEMATICS AND COMPUTING↗

Genetic Fusion of Thermoresponsive Polypeptides with UCST–type Behavior Mediates 1D Assembly of Coiled–Coil Bundlemers

Thermoresponsive resilin-like polypeptides (RLPs) of various lengths were genetically fused to two different computationally designed coiled coil-forming peptides with distinct thermal stability, to develop new strategies to assemble coiled coil peptides via temperature-triggered phase separation of the RLP units. Furthermore, their successful production in bacterial expression hosts was verified via gel electrophoresis, mass spectrometry, and amino acid analysis. Circular dichroism (CD) spectroscopy, ultraviolet-visible (UV/Vis) turbidimetry, and dynamic light scattering (DLS) measurements confirmed the stability of the coiled coils and showed that the thermosensitive phase behavior of the RLPs was preserved in the genetically fused hybrid polypeptides. Cryogenic-transmission electron microscopy and coarse-grained modeling revealed that functionalizing the coiled coils with thermoresponsive RLPs leads to their thermally triggered noncovalent assembly into nanofibrillar assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication of engineered dopant profiles in Er/Lu:YAG transparent laser ceramics via additive manufacturing

Transparent ceramic Er:YAG laser rods were fabricated via the direct ink write (DIW) method with engineered doping profiles featuring an Er-doped core with endcaps and core-clad structures. Laser rods up to 11 cm in length were produced which required development of a scalable process. To achieve this, multiple improvements were implemented, including printing the rods horizontally on a substrate, rather than vertically, eliminating the need for an external support structure and using a sacrificial drying layer to mitigate warping and defects. Highly transparent rods were achieved with optical scatter levels as low as 0.5%/cm (at 543 nm). A small refractive index difference of 5.7 ppm was measured at the interface between the Er-doped core and the Lu-doped endcaps and cladding. These results demonstrate DIW as a straightforward method for making good optical quality laser rods with engineered doping profiles to improve laser performance.

36 MATERIALS SCIENCE↗