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At least 1,261 records · Page 70

GJ 229B: Solving the Puzzle of the First Known T Dwarf with the APOLLO Retrieval Code

GJ 229B was the first T dwarf to be discovered in 1995, and its spectrum has been more thoroughly observed than that of most other brown dwarfs. Yet a full spectroscopic analysis of its atmosphere has not been done with modern techniques. This spectrum has several peculiar features, and recent dynamical estimates of GJ 229B’s mass and orbit have disagreed widely, both of which warrant closer investigation. With a separation of tens of astronomical units from its host star, GJ 229B falls near the border of the planet and stellar population formation regimes, so its atmosphere could provide clues to formation processes for intermediate objects of this type. In an effort to resolve these questions, we performed retrievals on published spectra of GJ 229B over a wide range of wavelengths (0.5–5.1 μm) using the open-source APOLLO code. Based on these retrievals, we present a more precise mass estimate of 41.6 ± 3.3MJ and an effective temperature estimate of 869 +5 −7 K, which are more consistent with evolutionary models for brown dwarfs and suggest an older age for the system of >1.0 Gyr. We also present retrieved molecular abundances for the atmosphere, including replicating the previously observed high CO abundance, and discuss their implications for the formation and evolution of this object. This retrieval effort will give us insight into how to study other brown dwarfs and directly imaged planets, including those observed with JWST and other next-generation telescopes.

Alex R Howe↗

Preliminary clustering properties of the DESI BGS bright targets using DR9 Legacy Imaging Surveys

ABSTRACT We characterize the selection cuts and clustering properties of a magnitude-limited sample of bright galaxies that is part of the Bright Galaxy Survey (BGS) of the Dark Energy Spectroscopic Instrument (DESI) using the ninth data release of the Legacy Imaging Surveys (DR9). We describe changes in the DR9 selection compared to the DR8 one and we also compare the DR9 selection in three distinct regions: BASS/MzLS in the north Galactic Cap (NGC), DECaLS in the NGC, and DECaLS in the south Galactic Cap (SGC). We investigate the systematics associated with the selection and assess its completeness by matching the BGS targets with the Galaxy and Mass Assembly (GAMA) survey. We measure the angular clustering for the overall bright sample (rmag ≤ 19.5) and as function of apparent magnitude and colour. This enables to determine the clustering strength r0 and slope γ by fitting a power-law model that can be used to generate accurate mock catalogues for this tracer. We use a counts-in-cells technique to explore higher order statistics and cross-correlations with external spectroscopic data sets in order to check the evolution of the clustering with redshift and the redshift distribution of the BGS targets using clustering redshifts. While this work validates the properties of the BGS bright targets, the final target selection pipeline and clustering properties of the entire DESI BGS will be fully characterized and validated with the spectroscopic data of Survey Validation.

79 ASTRONOMY AND ASTROPHYSICS↗

Validation Data Acquisition in HTTF during PCC Events

A validation experimental campaign was conducted in an Integral Effect Test (IET) facility of High Temperature Gas Reactors (HTGR), the High-Temperature Test Facility (HTTF) at Oregon State University (OSU). The HTTF simulates Depressurized and Pressurized Conduction Cooldowns (DCC and PCC). This campaign required the development of a new laser spectroscopic diagnostic to measure velocity in the challenging conditions of the HTTF: low speed (~1 m/s) gas flows at HTGR prototypical temperature and 1/10th pressure. This was a collaborative effort between co-PIs at The George Washington University (GW), Oregon State University (OSU), and NASA Langley Research Center. The main accomplishments of this project include the record for dynamic range for velocimetry, highest accuracy obtained with this technique, successful deployment in an IET leading to new validation matrix for CFD. These are detailed below and in manuscript appended to this executive summary. For this project, we introduced a new class of laser spectroscopic diagnostics to Thermal-Hydraulics to measure velocity of gases; furthermore, the diagnostic was demonstrated in-situ in an IET during DCC events. In such scenarios, particles used in mainstream techniques, like Particle Image Velocimetry (PIV) are not appropriate as they settle down too rapidly and also contaminate the experimental facility. Molecular tracers stay mixed within the working gas and can seed the flow in a technique called Molecular Tagging Velocimetry (MTV). In MTV a molecular tracer is photo-dissociated by a first (write) laser into radicals or molecules. The pattern created by the write laser is then interrogated with planar laser-induced fluorescence (PLIF), the read pulse(s), which are recorded with a camera. The pattern is probed and matched at two times (interval or probe time, dt), resulting in a time-of-flight velocimetry technique. This project demonstrated a new application range for MTV in gases. MTV has been extensively used for high-speed gas dynamics: molecules do not suffer from inertia associated with particles in regions of high accelerations (such as shock waves). For high-speed flows, the probe time is on the order of 0.1-10 µs. In time-of-flight techniques, the velocity is reconstructed from the recorded displacement, dx, between time interval dt: U = dx/dt. To first order, the resolution of the pattern matching is typically a (fixed) fraction of a pixel; therefore the resolution of the velocity measurement increases with dx and, for a given flow velocity, dt. For the low-speed flows of interest here, this requires long probe time, and therefore finding tracers that are stable for a long time. After an extensive literature survey we identified 6 tracers that would be suitable. We also worked with Spectra Physics to design a custom laser system that is flexible enough to probe these various tracers. The final instrument is made of 4 lasers that are integrated into a compact and movable cart to facilitate the deployment of the instrument off-site. One unique aspect of the laser system is the tunable dye laser (needed to do PLIF of the radicals). By being pumped by two Nd:YAG lasers, this laser is able to provide two pulses with any probe time (dt) for wavelengths between 200 and 900 nm with a linewidth of 3 pm. Accommodating the dual-pulse capability required customizing the pump lasers and the dye laser, making this system unique. Additionally, a custom UV-intensified CCD camera capable of frame-straddling and exposure time as short as 10 ns was acquired. More than two-third of the instrument cost (~$200k) was covered by a cost sharing from the PI’s startup funds. Of the 6 potential tracers identified, two were tested extensively (H2O and N2O) at high-temperature and elevated pressure at GW prior to conducting the tests at OSU. For both tracers, an Ar-F laser (193 nm, 10 ns, 10 mJ/pulse) photo-dissociates trace amounts (0.1 – 5% molar fraction) of the gases into OH and NO. OH is probed at 281.905 nm and NO at 226.186 nm (4-30mJ, 10 ns pulse). NO is very stable in inert environment and we could reconstruct velocities precisely with probe delay times as long at 40 ms, compared to 2 ms for OH, resulting in increased precision. Therefore, for the tests in the HTTF, N2O was selected as the final tracer and its optimal concentration was determined to be 0.5% molar. In the GW laboratory, we obtained a velocity measurement precision of 4 mm/s at conditions mimicking the HTTF tests. We also demonstrated the benefit of molecular tracers over particles and the flexibility of our instrument by continuously measuring velocity from 1000 to 0.1 m/s in a blow down test. This represents a dynamic range on velocity of 80 dB, which is unprecedented for velocimetry! Once the diagnostic was optimized, two two-week campaigns were conducted in the HTTF. This experimental campaign required numerous practical solutions to successfully and rapidly deploy this very sensitive table-top diagnostic in-situ. This was accomplished thanks to very extensive planning from all parties involved in the project. Due to constraints on availability of the HTTF, only adiabatic DCC tests were conducted. Specifically, the velocity was measured at the exit of the hot leg into the Reactor Cavity Simulation Tank (RCST). We were able to record the gas velocity associated with the air ingress for long times (up to one hour). Depending on the initial conditions (density of the gases in the Reactor Pressure Vessel and the RCST) the lock exchange lasted 30-60 s past the valve openings. Large vortices were identified within the shear layer at the interface of the cross flow. These vortices are an indication of shear-driven instability between the counter streams of different density. After the lock-exchange, a small residual flow was still present and its strength decayed exponentially. It finds its source in a buoyancy difference between the gases in both vessels due to the mixing and diffusion of the gases in the cross-over duct and the RPV lower plenum. We did not expect to capture this part of the transient, which would have been less significant (if not negligible) in the presence of a heated core; the precision of our measurement in the HTTF was 6 mm/s, which exceeded our expectations for such a complex test! Using commercial software (Fluent) we simulated the experiment with Computational Fluid Dynamic (CFD) using Reynolds Averaged Navier-Stokes (RANS) turbulence models. We were not able to accurately reproduce the shear layer instability, mixing, and diffusion captured in our experimental data, even with large 3D meshes (>10 M points). We attributed this to the inadequacy of the RANS models for the flow of interest: our experimental Reynolds number was too low and was outside the applicability range of the RANS models. Instead, we should have employed CFD with less modeling, such as Large Eddy (LES) or even Direct Numerical (DNS) simulations. Unfortunately, we did not have the computational resources to do so. Finally, it should be noted that this experimental technique holds great promises for measuring velocity in thermalhydraulics. MTV has an application domain (highlighted in the narrative) that is complimentary to more established (and simpler) techniques, such as PIV. It has attracted the attention of several thermalhydraulics researchers and sponsors to measure velocity in harsh environments. The spectroscopic nature of this technique also enables to expand it to measure temperature and concentration simultaneously to velocity. In lieu of a narrative, 4 detailed journal publications are appended to this executive summary to describe the various development and accomplishments during this project. They include 2 published manuscripts (Experiments in Fluids and Measurement Science and Technology), and two invited contributions following the NURETH-17 conference (Nuclear Science and Technology). Our current Nuclear Engineering and Design draft is not included at this time.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Iron speciation in blast furnace slag cements

Slag-containing pastes and concretes were analysed by element-specific synchrotron-based techniques to determine the speciation of iron on crushed materials through spatially resolved micro-spectroscopic studies. The investigated cement samples were hydrated either in the laboratory, or exposed to river or sea water. Metallic iron, along with minor proportions of iron sulphide and magnetite was detected in the laboratory sample. Iron sulphide, goethite, and siliceous hydrogarnet were discovered in the blended slag cements hydrated in contact with river water for up to 7 years. In contrast, no Fe(0) was observed in blended concretes exposed to sea water. Instead, iron sulphide, iron(II)-hydroxide and -oxide, hematite, magnetite, siliceous hydrogarnet, and goethite were detected as well as ilmenite (FeTiO{sub 3}) in the aggregates. The strong acceleration of Fe oxidation in samples exposed to sea water and the long-term passivation observed in the other samples indicate comparable processes as those occurring on steel bars.

36 MATERIALS SCIENCE↗

Synthesis, Crystal Structure, Hirshfeld Surface Analysis, DFT, and DNA-Binding Studies of (E)-2-(3-Hydroxy-4-Methoxybenzylidene)Hydrazinecarbothioamide

(E)-2-(3-Hydroxy-4-methoxybenzylidene)hydrazinecarbothioamide 3 was synthesized by reacting thiosemicarbazide with 2-hydorxy-3-methoxybenzaldehyde in dry ethanol. The structure was elucidated by spectroscopic (FT-IR, {sup 1}H NMR, and {sup 13}C NMR) and single crystal X-ray diffraction techniques. A detailed analysis of the intermolecular interactions has been performed based on the Hirshfeld surfaces and their associated two-dimensional fingerprint plots. DFT, spectroscopic, and electrochemical DNA-binding analysis confirmed that the compound is reactive to bind with DNA. Viscometric studies suggested that compound 3 has a mixed mode of interaction and intercalated into the DNA base pairs predominantly along with the possibility of electrostatic interactions. .

60 APPLIED LIFE SCIENCES↗

Synthesis and optical properties of polycrystalline Li{sub 2}Al{sub 2}B{sub 2}O{sub 7} (LABO)

A polycrystalline lithium aluminum borate (Li{sub 2}Al{sub 2}B{sub 2}O{sub 7}, LABO) has been synthesized by using simple solid-state technique. The obtained LABO polycrystalline was characterized by powder X-ray diffraction; Fourier transform infrared (FT-IR) spectroscopy and second harmonic generation (SHG) efficiency measurement. The functional groups were identified using the FT-IR spectroscopic data. The SHG efficiency of the polycrystalline material was obtained by the classic Kurtz powder technique using a fundamental wavelength 1064 nm of Nd:YAG laser and it is found to be 1.4 times that of potassium dihydrogen phosphate (KDP).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural and spectroscopic analyses of europium doped yttrium oxyfluoride powders prepared by combustion synthesis

A facile widely spread technique employed to produce low-cost high-yield oxide powders, combustion synthesis, was used to prepare yttrium oxyfluoride crystalline ceramic powders. The structure of the powders was analyzed by X-ray powder diffraction and Rietveld refinement. Samples heat treated at 700 °C had a predominance of vernier orthorhombic Y{sub 6}O{sub 5}F{sub 8} phase, while samples heat treated at 800 °C crystallized in stoichiometric rhombohedral YOF phase. The samples were doped with luminescent europium trivalent ions (Eu{sup 3+}) in different concentrations (1–15 wt.%) and Judd-Ofelt theory was used to probe the distortion from the inversion symmetry of the local crystal field and the degree of covalency between the rare-earth ion and the surrounding ligands. The luminescence lifetime was measured and the luminescence quantum efficiency (LQE) was estimated. We observed that Eu{sup 3+}:Y{sub 6}O{sub 5}F{sub 8} samples presented higher LQE in spite of the larger local crystal field anisotropy found for Eu{sup 3+}:YOF samples.

36 MATERIALS SCIENCE↗

Plasma Jet Printing and in Situ Reduction of Highly Acidic Graphene Oxide

Miniaturization of electronic devices and the advancement of Internet of Things pose exciting challenges to develop technologies for patterned deposition of functional nanomaterials. Printed and flexible electronic devices and energy storage devices can be embedded onto clothing or other flexible surfaces. Graphene oxide (GO) has gained much attention in printed electronics due its solution processability, robustness, and high electrical conductivity in the reduced state. We introduce an approach to print GO films from highly acidic suspensions with in situ reduction using an atmospheric pressure plasma jet. Low-temperature plasma of a He and H 2 mixture was used successfully to reduce a highly acidic GO suspension (pH < 2) in situ during deposition. This technique overcomes the multiple intermediate steps required to increase the conductivity of deposited GO. X-ray spectroscopic studies confirmed that the reaction intermediates and the concentration of oxygen functionalities bonded to GO have been reduced significantly by this approach without any additional steps. Moreover, the reduced GO films showed enhanced conductivity. Hence, this technique has a strong potential for printing conducting patterns of GO for a range of large-scale applications.

42 ENGINEERING↗

COSMOLOGY WITH PHOTOMETRICALLY CLASSIFIED TYPE Ia SUPERNOVAE FROM THE SDSS-II SUPERNOVA SURVEY

We present the cosmological analysis of 752 photometrically classified Type Ia Supernovae (SNe Ia) obtained from the full Sloan Digital Sky Survey II (SDSS-II) Supernova (SN) Survey, supplemented with host-galaxy spectroscopy from the SDSS-III Baryon Oscillation Spectroscopic Survey. Our photometric-classification method is based on the SN classification technique of Sako et al., aided by host-galaxy redshifts (0.05 < z < 0.55). SuperNova ANAlysis simulations of our methodology estimate that we have an SN Ia classification efficiency of 70.8%, with only 3.9% contamination from core-collapse (non-Ia) SNe. We demonstrate that this level of contamination has no effect on our cosmological constraints. We quantify and correct for our selection effects (e.g., Malmquist bias) using simulations. When fitting to a flat {Lambda}CDM cosmological model, we find that our photometric sample alone gives {Omega} {sub m} = 0.24{sup +0.07} {sub -0.05} (statistical errors only). If we relax the constraint on flatness, then our sample provides competitive joint statistical constraints on {Omega} {sub m} and {Omega}{sub {Lambda}}, comparable to those derived from the spectroscopically confirmed Three-year Supernova Legacy Survey (SNLS3). Using only our data, the statistics-only result favors an accelerating universe at 99.96% confidence. Assuming a constant wCDM cosmological model, and combining with H {sub 0}, cosmic microwave background, and luminous red galaxy data, we obtain w = -0.96{sup +0.10} {sub -0.10}, {Omega} {sub m} = 0.29{sup +0.02} {sub -0.02}, and {Omega} {sub k} = 0.00{sup +0.03} {sub -0.02} (statistical errors only), which is competitive with similar spectroscopically confirmed SNe Ia analyses. Overall this comparison is reassuring, considering the lower redshift leverage of the SDSS-II SN sample (z < 0.55) and the lack of spectroscopic confirmation used herein. These results demonstrate the potential of photometrically classified SN Ia samples in improving cosmological constraints.

79 ASTRONOMY AND ASTROPHYSICS↗

Cosmological Constraints from Multiple Probes in the Dark Energy Survey

The combination of multiple observational probes has long been advocated as a powerful technique to constrain cosmological parameters, in particular dark energy. The Dark Energy Survey has measured 207 spectroscopically confirmed type Ia supernova light curves, the baryon acoustic oscillation feature, weak gravitational lensing, and galaxy clustering. Here we present combined results from these probes, deriving constraints on the equation of state, w, of dark energy and its energy density in the Universe. Independently of other experiments, such as those that measure the cosmic microwave background, the probes from this single photometric survey rule out a Universe with no dark energy, finding w = -0.80(-0.11)(+0.09). The geometry is shown to be consistent with a spatially flat Universe, and we obtain a constraint on the baryon density of Omega(b) = 0.069(-0.012)(+0.009) that is independent of early Universe measurements. These results demonstrate the potential power of large multiprobe photometric surveys and pave the way for order of magnitude advances in our constraints on properties of dark energy and cosmology over the next decade.

Abbott, T. M. C.↗

Development of a High-Pressure Gaseous Burner for Calibrating Optical Diagnostic Techniques

In this work-in-progress report, we show the development of a unique high-pressure burner facility (up to 60 atm) that provides steady, reproducible premixed flames with high precision, while having the capability to use multiple fuel/oxidizer combinations. The highpressure facility has four optical access ports for applying different laser diagnostic techniques and will provide a standard reference flame for the development of a spectroscopic database in high-pressure/temperature conditions. Spontaneous Raman scattering (SRS) was the first diagnostic applied, and was used to successfully probe premixed hydrogen-air flames generated in the facility using a novel multi-jet micro-premixed array burner element. The SRS spectral data include contributions from H2, N2, O2, and H2O and were collected over a wide range of equivalence ratios ranging from 0.16 to 4.9 at an initial pressure of 10-atm via a spatially resolved point SRS measurement with a high-performance optical system. Temperatures in fuel-lean to stoichiometric conditions were determined from the ratio of the Stokes to anti-Stokes scattering of the Q-branch of N2, and those in fuel-rich conditions via the rotational temperature of H2. The SRS derived temperatures using both techniques were consistent and indicated that the flame temperature was approximately 500 K below that predicted by adiabatic equilibrium, indicating a large amount of heat-loss at the measurement zone. The integrated vibrational SRS signals show that SRS provides quantitative number density data in high-pressure H2-air flames.

Kojima, Jun↗

Probing spectroscopic like information using resonant scattering

Resonant x-ray scattering can combine layer sensitivity of reflectivity technique with short-range structural sensitivity of absorption technique due to element specificity and contrast variation mechanism of resonant effect. We demonstrated the idea through depth profile study of chemical composition of multi-element thin film system at soft x-ray spectral range near boron K-absorption edge.

36 MATERIALS SCIENCE↗

Progress on a Rayleigh Scattering Mass Flux Measurement Technique

A Rayleigh scattering diagnostic has been developed to provide mass flux measurements in wind tunnel flows. Spectroscopic molecular Rayleigh scattering is an established flow diagnostic tool that has the ability to provide simultaneous density and velocity measurements in gaseous flows. Rayleigh scattered light from a focused 10 Watt continuous-wave laser beam is collected and fiber-optically transmitted to a solid Fabry-Perot etalon for spectral analysis. The circular interference pattern that contains the spectral information that is needed to determine the flow properties is imaged onto a CCD detector. Baseline measurements of density and velocity in the test section of the 15 cm x 15 cm Supersonic Wind Tunnel at NASA Glenn Research Center are presented as well as velocity measurements within a supersonic combustion ramjet engine isolator model installed in the tunnel test section.

Mielke-Fagan, Amy F.↗

V IV O and V IV Species Formed in Aqueous Solution by the Tridentate Glutaroimide–Dioxime Ligand – An Instrumental and Computational Characterization

Complexation of V IV in aqueous solution with glutaroimide–dioxime (H 3 L), a ligand proposed for the possible sequestration of uranium from seawater, was studied by the combined application of spectroscopic (EPR and UV/Vis), spectrometric (ESI‐MS), electrochemical (CV), and computational (DFT) techniques. The results indicate that a rare non‐oxido V IV species, with formula [V IV L 2 ] 2– , is formed in the pH range 3–5. It transforms into a usual V IV O complex, [V IV OL(OH)] 2– , at pH > 6. The non‐oxido species is characterized by a “ type 3 ” EPR spectrum with A z ≈ 126 × 10 –4 cm –1 and a UV/Vis signal with ε > 2000 m –1 cm –1 in the visible region. The detection of V V species by ESI‐MS spectrometry was related to two possible oxidation processes, the first one in solution and the second one in‐source during the recording of the spectra. The cyclic voltammogram of [V IV L 2 ] 2– shows two quasi‐reversible processes, at E 1/2 = –0.75 V and E 1/2 = 0.03 V, assigned to the V IV /V III reduction and V IV /V V oxidation, respectively. All the experimental results were verified by DFT calculations, which indicated that the geometry of the non‐oxido V IV complex is intermediate between an octahedron and a trigonal prism and allowed us to predict its 51 V hyperfine coupling (HFC) tensor A , the electron absorption spectrum, the two redox processes in the cyclic voltammogram, and the electronic structure that, in turn, determines its EPR and UV/Vis behavior.

Sanna, Daniele↗

Kβ X-ray Emission Spectroscopy as a Probe of Cu(I) Sites: Application to the Cu(I) Site in Preprocessed Galactose Oxidase

Cu(I) active sites in metalloproteins are involved in O 2 activation, but their O 2 reactivity is difficult to study due to the Cu(I) d 10 closed shell which precludes the use of conventional spectroscopic methods. Kβ X-ray emission spectroscopy (XES) is a promising technique for investigating Cu(I) sites as it detects photons emitted by electronic transitions from occupied orbitals. Here, we demonstrate the utility of Kβ XES in probing Cu(I) sites in model complexes and a metalloprotein. Using Cu(I)Cl, emission features from double-ionization (DI) states are identified using varying incident X-ray photon energies, and a reasonable method to correct the data to remove DI contributions is presented. Kβ XES spectra of Cu(I) model complexes, having biologically relevant N/S ligands and different coordination numbers, are compared and analyzed, with the aid of density functional theory (DFT) calculations, to evaluate the sensitivity of the spectral features to the ligand environment. While the low-energy Kβ 2,5 emission feature reflects the ionization energy of ligand np valence orbitals, the high-energy Kβ 2,5 emission feature corresponds to transitions from molecular orbitals (MOs) having mainly Cu 3d character with the intensities determined by ligand-mediated d–p mixing. A Kβ XES spectrum of the Cu(I) site in preprocessed galactose oxidase (GO pre ) supports the 1Tyr/2His structural model that was determined by our previous X-ray absorption spectroscopy and DFT study. Finally, the high-energy Kβ 2,5 emission feature in the Cu(I)-GO pre data has information about the MO containing mostly Cu 3d x 2 –y 2 character that is the frontier molecular orbital (FMO) for O 2 activation, which shows the potential of Kβ XES in probing the Cu(I) FMO associated with small-molecule activation in metalloproteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Newly Synthesized Heteronuclear Ruthenium(II)/Ferrocene Complexes Suppress the Growth of Mammary Carcinoma in 4T1-Treated BALB/c Mice by Promoting Activation of Antitumor Immunity

The two new heterometallic Ru(II)-tpy/ferrocene complexes [Ru(tpy)Cl2(mtefc)] (1) and [Ru(tpy)Cl2(mtpfc)] (2) (where tpy = 2,2′:6′,2′′-terpyridine, mtefc = (2-(methylthio)ethyl)ferrocene, and mtpfc = (3-(methylthio)propyl)ferrocene) have been synthesized and then characterized through elemental analysis, followed by various spectroscopic (IR, UV-vis, 1D and 2D NMR) and mass spectrometric techniques (MALDI TOF and ESI Q-TOF MS). UV-vis and fluorescence spectroscopy and viscometry were employed to study the interactions of the complexes 1 and 2 with calf thymus DNA. Both 1 and 2 expelled ethidium bromide (EB) from the EB/DNA complex (Ksv = (1.5-1.8) × 104 M-1), which suggested that the complexes intercalated into the double helix of DNA. Both complexes strongly quenched the fluorescence of tryptophan residues in serum albumin through both static and dynamic quenching. Molecular docking confirmed the intercalative mode of complex interaction with DNA. The docking results implied that 1 and 2 interacted with hydrophobic residues of albumin, particularly with those lying in the proximity of Tyr 160. We here demonstrate the high cytotoxic potential of complexes 1 and 2 against the breast cancer cells that originated either from humans (MDA-MB-231) or from mice (4T1), with apoptosis being the main mechanism of complex-induced cell death. It is worth noting that both complexes promoted activation of innate and acquired antitumor immunity, which contributed to the reduced growth and progression of mammary carcinoma in vivo. Copyright © 2018 American Chemical Society.

60 APPLIED LIFE SCIENCES↗

Far-field probing of leaky topological states in all-dielectric metasurfaces

Topological phase transitions in condensed matter systems give rise to exotic states of matter such as topological insulators, superconductors, and superfluids. Photonic topological systems open a whole new realm of research and technological opportunities, exhibiting a number of important distinctions from their condensed matter counterparts. Photonic modes can leak into free space, which makes it possible to probe topological photonic phases by spectroscopic means via Fano resonances. Based on this idea, we develop a technique to retrieve the topological properties of all-dielectric metasurfaces from the measured far-field scattering characteristics. Collected angle-resolved spectra provide the momentum-dependent frequencies and lifetimes of the photonic modes that enable the retrieval of the effective Hamiltonian and extraction of the topological invariant. Our results demonstrate how the topological states of open non-Hermitian systems can be explored via far-field measurements, thus paving a way to the design of metasurfaces with unique scattering characteristics controlled via topological effects.

42 ENGINEERING↗

Sulfur Kβ X-ray emission spectroscopy: comparison with sulfur K-edge X-ray absorption spectroscopy for speciation of organosulfur compounds

Until recently, sulfur was known as a “spectroscopically silent” element because of a paucity of convenient spectroscopic probes suitable for in situ chemical speciation. In recent years the technique of sulfur K-edge X-ray absorption spectroscopy (XAS) has been used extensively in sulfur speciation in a variety of different fields. With an initial focus on reduced forms of organic sulfur, we have explored a complementary X-ray based spectroscopy – sulfur Kβ X-ray emission spectroscopy (XES) – as a potential analytical tool for sulfur speciation in complex samples. In this work, we compare and contrast the sensitivity of sulfur Kβ XES with that of sulfur K-edge XAS, and find differing sensitivities for the two techniques. In some cases an approach involving both sulfur K-edge XAS and sulfur Kβ XES may be a powerful combination for deducing sulfur speciation in samples containing complex mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗