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At least 145 records · Page 8

Symmetry Breaking in Tetrahedral Chiral Plasmonic Nanoparticle Assemblies

Self-assembled plasmonic structures combine the specificity and tunability of chemical synthesis with collective plasmonic properties. In this work we systematically explore the effects of symmetry breaking on the chiroptical response of an assembly of plasmonic nanoparticles using simulation. The design is based on a tetrahedral nanoparticle frame with two different types of nanoparticles, where chirality is induced by targeted stimuli that change the distance along one edge of the assembly. Here, we show that the intensity, spectral position, and handedness of the CD response are tunable with small structural changes, making it usable as a nanoscale plasmonic ruler. We then build upon this initial design to show that the symmetry breaking principle may also be used to design a chiral pyramid using a mixture of different nanoparticle materials, which affords tunability over a broad spectral range, and retrieves nanoscale conformational changes over a range of length scales.

36 MATERIALS SCIENCE↗

Diffusion of Small He Clusters in Bulk and Grain Boundaries in α-Fe

The diffusion properties of He interstitials and He clusters in the bulk and grain boundaries (GBs) of α-Fe have been studied using molecular dynamics with a newly developed Fe-He potential. The low migration energy barrier for a single He interstitial in the bulk is consistent with that obtained using ab initio methods. Small He clusters can migrate at low temperatures, but at higher temperatures they will kick out a self-interstitial atom (SIA) and become trapped by the vacancy, forming an He-vacancy complex. It is of great interest to note that small Henvacancy clusters (n<5) in the bulk are able to absorb an SIA, and the clusters become mobile again. Trapping and de-trapping of He clusters by emitting and absorbing an SIA represent an important dynamic process that provides a mechanism for the diffusion of He clusters and the nucleation of He bubbles in bulk Fe, particularly under irradiation in which numerous SIAs and vacancies are constantly being produced. A single He interstitial can migrate one-dimensionally or two-dimensionally within GBs, depending on the GB structure. Small interstitial Hen clusters 2 (n ~ 1 - 10) can easily kick out an SIA, and become trapped by the vacancy, while the SIA quickly diffuses away from the clusters, disappearing into the GB, such that de-trapping of the He clusters by absorbing an SIA is less likely to occur. This suggests that small He clusters may be treated as relatively immobile defects in GBs. The different behavior of He clusters in the bulk compared to their behavior in GBs may explain the different He bubble sizes experimentally observed in the bulk and in GBs in reduced activation ferritic/martensitic steels that have been simultaneously neutron irradiated and He implanted.

Computer simulations↗

Experimental and theoretical insight into the soot tendencies of the methylcyclohexene isomers

The formation of soot precursors during combustion of three positional isomers of methylcyclohexene was investigated in flow reactor experiments and through density functional theory simulations. As evidenced by a recently published structure-property model, the sooting tendencies of these compounds differ from those of structurally similar molecules - suggesting new or unusual reaction chemistry. It was demonstrated that 1-methyl-1-cyclohexene and 4-methyl-1-cyclohexene preferentially react via a retro-Diels-Alder pathway leading to ring opening and molecular weight reduction. 3-methyl-1-cyclohexene, which exhibits much higher yield sooting index, preferentially reacts via dehydrogenation to cyclohexadienes and toluene - consistent with higher soot formation. It was demonstrated that the relative stability of the first radical intermediate plays a considerable role in determining the branching ratio between formation of soot precursors and ring opened retro-Diels-Alder reaction products. This study underscores the importance that small structural features can have in determining the ultimate fate of carbon during combustion processes.

09 BIOMASS FUELS↗

SU-E-J-129: Atlas Development for Cardiac Automatic Contouring Using Multi-Atlas Segmentation

Purpose: To develop a set of atlases for automatic contouring of cardiac structures to determine heart radiation dose and the associated toxicity. Methods: Six thoracic cancer patients with both contrast and non-contrast CT images were acquired for this study. Eight radiation oncologists manually and independently delineated cardiac contours on the non-contrast CT by referring to the fused contrast CT and following the RTOG 1106 atlas contouring guideline. Fifteen regions of interest (ROIs) were delineated, including heart, four chambers, four coronary arteries, pulmonary artery and vein, inferior and superior vena cava, and ascending and descending aorta. Individual expert contours were fused using the simultaneous truth and performance level estimation (STAPLE) algorithm for each ROI and each patient. The fused contours became atlases for an in-house multi-atlas segmentation. Using leave-one-out test, we generated auto-segmented contours for each ROI and each patient. The auto-segmented contours were compared with the fused contours using the Dice similarity coefficient (DSC) and the mean surface distance (MSD). Results: Inter-observer variability was not obvious for heart, chambers, and aorta but was large for other structures that were not clearly distinguishable on CT image. The average DSC between individual expert contours and the fused contours were less than 50% for coronary arteries and pulmonary vein, and the average MSD were greater than 4.0 mm. The largest MSD of expert contours deviating from the fused contours was 2.5 cm. The mean DSC and MSD of auto-segmented contours were within one standard deviation of expert contouring variability except the right coronary artery. The coronary arteries, vena cava, and pulmonary vein had DSC<70% and MSD>3.0 mm. Conclusion: A set of cardiac atlases was created for cardiac automatic contouring, the accuracy of which was comparable to the variability in expert contouring. However, substantial modification may need for auto-segmented contours of indistinguishable small structures.

60 APPLIED LIFE SCIENCES↗

Convergence of small scale Ly α structure at high- z under different reionization scenarios

ABSTRACT The Ly α forest (LAF) at z > 5 probes the thermal and reionization history of the intergalactic medium (IGM) and the nature of dark matter, but its interpretation requires comparison to cosmological hydrodynamical simulations. At high-z, convergence of these simulations is more exacting since transmission is dominated by underdense voids that are challenging to resolve. With evidence mounting for a late end to reionization, small structures down to the sub-kpc level may survive to later times than conventionally thought due to the reduced time for pressure smoothing to impact the gas, further tightening simulation resolution requirements. We perform a suite of simulations using the Eulerian cosmological hydrodynamics code Nyx, spanning domain sizes of 1.25 − 10 h−1 Mpc and 5 − 80 h−1 kpc cells, and explore the interaction of these variables with the timing of reionization on the properties of the matter distribution and the simulated LAF at z = 5.5. In observable Ly α power, convergence within 10 per cent is achieved for k < 0.1 s km–1, but larger k shows deviation of up to 20 per cent. While a later reionization retains more small structure in the density field, because of the greater thermal broadening there is little difference in the convergence of LAF power between early (z = 9) and later (z = 6) reionizations. We conclude that at z ∼ 5.5, resolutions of 10 kpc are necessary for convergence of LAF power at k < 0.1 s km–1, while higher-k modes require higher resolution, and that the timing of reionization does not significantly impact convergence given realistic photoheating.

79 ASTRONOMY AND ASTROPHYSICS↗

ESI-MS of Cucurbituril Complexes Under Negative Polarity

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool to study host–guest supramolecular interactions. ESI-MS can be used for detailed gas-phase reactivity studies, to clarify the structure, or simply to verify the formation of complexes. Depending on the structure of the host and of the guest, negative and/or positive ESI are used. Here we report the unexpected formation of host–guest complexes between cucurbit[n]urils (n = 7, 8, CB[n]) and amine, styryl pyridine, and styryl pyridine dimer cations, under negative ESI. Non-complexed CB[n] form double charged halide (Br{sup -}, Cl{sup -}, F{sup -}) adducts. Under negative ESI, halide ions interact with CB[n] outer surface hydrogen atoms. One to one host–guest complexes (1:1) of CB[n] with positive charged guests were also observed as single and double charged ions under negative ESI. The positive charge of guests is neutralized by ion-pairing with halide anions. Depending on the number of positive charges guests retain in the gas phase, one or two additional halide ions are required for neutralization. Complexes 1:2 of CB[8] with styryl pyridines retain two halide ions in the gas phase, one per guest. Styryl pyridine dimers form 1:1 complexes possessing a single extra halide ion and therefore a single positive charge. Negative ESI is sensitive to small structural differences between complexes, distinguishing between 1:2 complexes of styryl pyridine-CB[8] and corresponding 1:1 complexes with the dimer. Negative ESI gives simpler spectra than positive ESI and allows the determination of guest charge state of CB[n] complexes in the gas phase. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Non-destructive characterisation of polymers and Al-alloys by polychromatic cone-beam phase contrast tomography

X-ray computed tomography (XCT) has become a very important tool for the non-destructive characterisation of materials. Continuous improvements in the quality and performance of X-ray tubes and detectors have led to cone-beam XCT systems that can now achieve spatial resolutions down to 1 {mu}m and even below. Since not only the amplitude but also the phase of an X-ray beam is altered while passing through an object, phase contrast effects can occur even for polychromatic sources when the spatial coherence due to a small focal spot size is high enough. This can lead to significant improvements over conventional attenuation-based X-ray computed tomography. Phase contrast can increase by edge enhancement the visibility of small structures and of features which are only slightly different in attenuation. We report on the possibilities of polychromatic cone-beam phase contrast tomography for non-destructive characterisation of materials. A carbon fibre-reinforced polymer and the Al-alloys AlMg5Si7 and AlSi18 were investigated with high resolution cone-beam X-ray computed tomography with a polychromatic tube source. Under certain conditions strong phase contrast resulting in an upward and downward overshooting of the grey values across edges was observed. The phase effects are much stronger for the polymer than for the Al-alloys. The influence on the phase contrast of the parameters, including source-detector distance, focal spot size and tube acceleration voltage is presented. Maximum phase contrast was observed for a maximum distance between the source and the detector, for a low voltage and a minimum focal spot size at the X-ray source. The detectability of the different phases is improved by the edge enhancement and the resulting improvement of sharpness. Thus, a better segmentation of the carbon fibres in the fibre-reinforced polymer and of the Mg{sub 2}Si-phase in the AlMg5Si7-alloy is achieved. Primary and eutectic Si cannot be detected by attenuation-based X-ray computed tomography due to the small difference in X-ray attenuation between the Si and the Al-matrix in AlSi18. However, phase contrast effects lead to a significant detectability and the large primary Si particles become clearly visible in the tomograms of AlSi18. - Highlights: Black-Right-Pointing-Pointer Phase contrast increases with increasing distance object-detector and with decreasing U, X-ray spot. Black-Right-Pointing-Pointer The detectability of details is improved by the phase contrast. Black-Right-Pointing-Pointer For the carbon fibre-reinforced polymer the visibility of the carbon fibres is improved. Black-Right-Pointing-Pointer For AlMg5Si7 the detectability of the phases Fe-aluminides and Mg{sub 2}Si particles is improved. Black-Right-Pointing-Pointer For AlSi18 primary Si particles with a size > 50 {mu}m become detectable because of the phase contrast.

36 MATERIALS SCIENCE↗

Incorporation of Membrane Proteins Into Bicontinuous Microemulsions Through Winsor‐III System‐Based Extraction

Abstract The membrane proteins (MP) α‐synuclein (ASYN) and bacteriorhodopsin (BR) were readily incorporated into bicontinuous microemulsions (BμEs) formed by two microemulsion systems: water/heptane/Aerosol‐OT (AOT)/CK‐2,13 and water/dodecane/sodium dodecyl sulfate (SDS)/1‐pentanol. (CK‐2,13 is an alkyl ethoxylate possessing two alkyl tail groups of carbon chain length 2 and 13 and an average degree of ethoxylation of 5.6.) MP were encapsulated in BμEs through preparation of Winsor‐III systems at optimal salinity, with the anionic surfactants AOT and SDS providing the driving force for extraction. Dissolution of ASYN in BμEs greatly increased the former's α‐helicity, similar to ASYN's behavior in the presence of biomembranes, while BμE‐ and vesicle‐encapsulated BR possessed similar secondary structure. Small‐angle neutron scattering (SANS) results clearly demonstrated the direct interaction of MP with the surfactants, resulting in a decrease of surface area per volume for surfactant monolayers due to decreased surfactant efficiency. The SANS signal for ASYN was isolated through the use of neutron contrast matching for the surfactants through partial deuteration of water and oil, one of the first reports of contrast matching for BμEs in the literature. The SANS results of the contrast‐matched sample reflected similar aggregation for ASYN in BμEs as was reported previously for vesicles and SDS solution. This study demonstrates the potential use of BμEs as MP host systems for conducting biochemical reactions such as the conversion of sunlight into adenosine triphosphate by BR and studying the fundamental behavior of MP, such as the role of ASYN dysfunction in Parkinson's disease, as well as for isolation and purification of MP via Winsor‐III‐based extraction.

Hayes, Douglas G.↗

Empirical performance bounds for quantum approximate optimization

The quantum approximate optimization algorithm (QAOA) has been put forth as a method for near-term quantum computers to solve optimization problems. However, assessments of QAOA performance have mostly focused on small structured problem instances while performance on more general instances is less clear. Here, we numerically simulate QAOA pure state dynamics for every instance of MaxCut on non-isomorphic unweighted graphs with nine or fewer vertices with depth parameters p ≤ 3. We find the approximation ratios and optimized circuit parameters concentrate across graphs of a given size and empirically show increases in concentration as graph size increases. The parameter concentration leads to two median-angle heuristics that overcome difficulties in QAOA parameter optimization and obtain mean approximation ratios within 3% and 0.2% of the optimal. We also analyze the probability to measure an optimal solution and find increasing variations between graphs as depth increases, in stark contrast to the approximation ratios which concentrate as depth increases. Furthermore, the resulting benchmark data set gives empirical bounds for on-going experimental realizations and lays groundwork for theoretical extensions to greater problem sizes and depths where QAOA may prove important for practically relevant problems.

79 ASTRONOMY AND ASTROPHYSICS↗

Subgrid-scale model for radiative transfer in turbulent participating media

The simulation of turbulent flows of radiating gases, taking into account all turbulence length scales with an accurate radiation transport solver, is computationally prohibitive for high Reynolds or Rayleigh numbers. This is particularly the case when the small structures are not optically thin. We develop in this paper a radiative transfer subgrid model suitable for the coupling with direct numerical simulations of turbulent radiating fluid flows. Owing to the linearity of the Radiative Transfer Equation (RTE), the emission source term is spatially filtered to define large-scale and subgrid-scale radiation intensities. The large-scale or filtered intensity is computed with a standard ray tracing method on a coarse grid, and the subgrid intensity is obtained analytically (in Fourier space) from the Fourier transform of the subgrid emission source term. A huge saving of computational time is obtained in comparison with direct ray tracing applied on the fine mesh. Model accuracy is checked for three 3D fluctuating temperature fields. The first field is stochastically generated and allows us to discuss the effects of the filtering level and of the optical thicknesses of the whole medium, of the integral length scale, and of the cutoff wave length. The second and third cases correspond respectively to turbulent natural convection of humid air in a cubical box, and to the flow of hot combustion products inside a channel. In all cases, the achieved accuracy on radiative powers and wall fluxes is about a few percents.

42 ENGINEERING↗

Divalent europium doped CaF 2 and BaF 2 nanocrystals from ionic liquids

A new, facile and quick synthesis method for Eu 2+ doped the alkaline earth fluorides was developed using ionic liquids as solvent, precursor and capping agent. Reductive atmosphere and very high temperatures were avoided, while still attaining the desired structure, small particle sizes and divalent oxidation state of the lanthanide. Here, this opens the door for the development of new Ln 2+ doped nanomaterials. Here, the successful Eu 2+ incorporation was proven by optical spectroscopic measurements which showed the spin and parity allowed f-d transitions of Eu 2+ in CaF 2 :Eu 2+ /BaF 2 :Eu 2+ . 4f 7 -4f 7 transitions could be observed at low temperatures (7 K).

36 MATERIALS SCIENCE↗

Nanocavity-Enhanced Giant Stimulated Raman Scattering in Si Nanowires in the Visible Light Region

Silicon photonics has been a very active area of research especially in the past two decades in order to meet the ever-increasing demand for more computational power and faster device speeds and their natural compatibility with complementary metal-oxide semiconductor. In order to develop Si as a useful photonics material, essential photonic components such as light sources, waveguides, wavelength convertors, modulators, and detectors need to be developed and integrated. However, due to the indirect electronic bandgap of Si, conventional light emission devices such as light-emitting diodes and lasers cannot be built. Therefore, there has been considerable interest in developing Si-based Raman lasers, which are nonlinear devices and require large stimulated Raman scattering (SRS) in an optical cavity. However, due to the low quantum yield of SRS in Si, Raman lasers have very large device footprints and high lasing threshold, making them unsuitable for faster, smaller, and energy-efficient devices. Here in this paper, we report strong SRS and extremely high Raman gain in Si nanowire optical cavities in the visible region with measured SRS threshold as low as 30 kW/cm 2 . At cavity mode resonance, light is confined into a low mode volume and high intensity electromagnetic mode inside the Si nanowire due to its high refractive index, which leads to strong SRS at low pump intensities. Electromagnetic calculations reveal greater than 6 orders of magnitude increase in Raman gain coefficient at 532 nm pump wavelength, compared to the gain value at 1.55 μm wavelength reported in literature, despite the 10 8 higher losses at 532 nm. Because of the high gain in such small structures, we believe that this is a significant first step in realizing a monolithically integrable nanoscale low-powered Si Raman laser.

36 MATERIALS SCIENCE↗

Highly Selective Methane to Methanol Conversion on Inverse SnO 2 /Cu 2 O/Cu(111) Catalysts: Unique Properties of SnO 2 Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane

Direct methane to methanol (CH 4 → CH 3 OH) conversion in heterogeneous catalysis has been a long-standing challenge due to the difficulties in equalizing the activation of methane and protection of the methanol product at the same reaction conditions. Here, we report an inverse catalyst, consisting of small structures of SnO 2 (0.5-1 nm in size) dispersed on Cu 2 O/Cu(111), for highly selective CH 3 OH production from CH 4 . This system was investigated by combining theoretical [density functional theory calculations (DFT), kinetic Monte Carlo simulations (KMC)] and experimental methods [scanning tunneling microscopy (STM), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)]. The DFT and AP-XPS studies showed that on SnO 2 /Cu 2 O/Cu(111) the conversion of CH 4 by oxygen (O 2 ) preferred complete combustion to carbon dioxide (CO 2 ). The addition of water (H 2 O) enhanced the production of CH 3 OH to nearly 100% selectivity in KMC simulations. This trend was consistent with results of AP-XPS. The presence of water in the reaction environment rendered an extremely high amount of methoxy species (*CH 3 O), a precursor for CH 3 OH production. Further, the high CH 3 OH selectivity of SnO 2 /Cu 2 O/Cu(111) reflected the unique atomic and electronic structure of the supported SnO 2 nanoparticles. As a result, the O 2 adsorption and dissociation, and thus the full combustion of CH 4 to CO 2 , was completely suppressed; while the H 2 O dissociative adsorption was still feasible, providing active hydroxyl species for a truly selective CH 4 to CH 3 OH conversion.

03 NATURAL GAS↗

Lateral Integration of SnS and GeSe van der Waals Semiconductors: Interface Formation, Electronic Structure, and Nanoscale Optoelectronics

The emergence of atomically thin crystals has allowed extending materials integration to lateral heterostructures where different 2D materials are covalently connected in the plane. The concept of lateral heterostructures can be generalized to thicker layered crystals, provided that a suitably faceted seed crystal presents edges to which a compatible second van der Waals material can be attached layer by layer. Here, we examine the possibility of integrating multilayer crystals of the group IV monochalcogenides SnS and GeSe, which have the same crystal structure, small lattice mismatch, and similar bandgaps. In a two-step growth process, lateral epitaxy of GeSe on the sidewalls of multilayer SnS flakes (obtained by vapor transport of a SnS 2 precursor on graphite) yields heterostructures of laterally stitched crystalline GeSe and SnS without any detectable vertical overgrowth of the SnS seeds and with sharp lateral interfaces. Combined cathodoluminescence spectroscopy and ab initio calculations show the effects of small band offsets on carrier transport and radiative recombination near the interface. Further, the results demonstrate the possibility of forming atomically connected lateral interfaces across many van der Waals layers, which is promising for manipulating optoelectronics, photonics, and for managing charge- and thermal transport.

2D layered crystals↗

Giant Concentric Metallosupramolecule with Aggregation-Induced Phosphorescent Emission

Fluorescent metallo-supramolecules have received considerable attention due to their precisely-controlled dimensions as well as the tunable photophysical and photochemical properties. However, phosphorescent analogues are still rare, and limited to small structures with low-temperature phosphorescence. In this work, we report the self-assembly and photophysical studies of a giant, discrete metallo-supramolecular concentric hexagon functionalized with six alkynylplatinum(II) bzimpy moieties. With a size larger than 10 nm and molecular weight higher than 26,000 Da, the assembled terpyridine-based supramolecule displayed phosphorescent emission at room temperature. Moreover, the supramolecule exhibited enhanced aggregation-induced phosphorescent emission compared to the ligand by tuning the aggregation states through intermolecular interactions, and significant enhancement of emission to CO 2 gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revisiting Conversion Reaction Mechanisms in Lithium Batteries: Lithiation-Driven Topotactic Transformation in FeF 2

Intercalation-type electrodes have now been commonly employed in today’s batteries as such materials are capable of storing and releasing lithium reversibly via topotactic transformation, conducive to small structural change, but they have limited interstitial sites to hold Li. In contrast, conversion electrodes feature high Li-storage capacity, but often undergo large structural change during (de)lithiation, resulting in cycling instability. One exception is iron fluoride (FeF 2 ), a conversion-type cathode that exhibits both high capacity and high cycling stability. Herein, we report a lithiation-driven topotactic transformation in a single crystal of FeF2, unveiled by in situ visualization of the spatial and crystallographic correlation between the parent and converted phases. Specifically, conversion in FeF 2 resembles the intercalation process but involves transport of both Li + and Fe 2+ ions within the F-anion array, leading to formation of Fe preferentially along specific crystallographic orientations of FeF 2 . Throughout the process, the F-anion framework is retained, creating a checkerboard-like structure, within which the volume change is largely compensated, thereby enabling the high cyclability in FeF 2 . Lastly, findings from this study, with unique insights into conversion reaction mechanisms, may help to pave the way for designing conversion-type electrodes for the next-generation high energy lithium batteries.

25 ENERGY STORAGE↗

Anti-Hermitian photodetector facilitating efficient subwavelength photon sorting

The ability to split an incident light beam into separate wavelength bands is central to a diverse set of optical applications, including imaging, biosensing, communication, photocatalysis, and photovoltaics. Entirely new opportunities are currently emerging with the recently demonstrated possibility to spectrally split light at a subwavelength scale with optical antennas. Unfortunately, such small structures offer limited spectral control and are hard to exploit in optoelectronic devices. Here, we overcome both challenges and demonstrate how within a single-layer metafilm one can laterally sort photons of different wavelengths below the free-space diffraction limit and extract a useful photocurrent. This chipscale demonstration of anti-Hermitian coupling between resonant photodetector elements also facilitates near-unity photon-sorting efficiencies, near-unity absorption, and a narrow spectral response (~30 nm) for the different wavelength channels. This work opens up entirely new design paradigms for image sensors and energy harvesting systems in which the active elements both sort and detect photons.

36 MATERIALS SCIENCE↗

Mechanism of DNA origami folding elucidated by mesoscopic simulations

Abstract Many experimental and computational efforts have sought to understand DNA origami folding, but the time and length scales of this process pose significant challenges. Here, we present a mesoscopic model that uses a switchable force field to capture the behavior of single- and double-stranded DNA motifs and transitions between them, allowing us to simulate the folding of DNA origami up to several kilobases in size. Brownian dynamics simulations of small structures reveal a hierarchical folding process involving zipping into a partially folded precursor followed by crystallization into the final structure. We elucidate the effects of various design choices on folding order and kinetics. Larger structures are found to exhibit heterogeneous staple incorporation kinetics and frequent trapping in metastable states, as opposed to more accessible structures which exhibit first-order kinetics and virtually defect-free folding. This model opens an avenue to better understand and design DNA nanostructures for improved yield and folding performance.

77 NANOSCIENCE AND NANOTECHNOLOGY↗