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At least 379 records · Page 21

Esterification of 3-quinuclidinol, a marker for the incapacitant BZ, for analysis by EI-GC-MS in OPCW test matrices

The analysis by EI-GC-MS of 3-quinuclidinol (3Q), a marker for the riot control and incapacitating agent quinuclinidyl benzilate (BZ), using several, new acylation strategies is described. After evaluating and optimizing conditions for the acylations, these were tested on their ability to successfully derivatize 3Q in three different matrices featured in the 44th Organisation for the Prohibition of Chemical Weapons (OPCW) proficiency test (PT). As 3Q is a highly polar compound, the work here describes acylation strategies that generate 3Q analogs with superior gas chromatographic profiles relative to the underivatized material. The acyl groups studied in this work included acetyl, benzoyl, pentafluorobenzoyl and the bis(3,5-trifluoromethyl)benzoyl. The acylated 3Q products provide sharp, detectable peaks with significantly different retention times from that of the unmodified 3Q. Thus, the retention times for acetyl-, benzoyl-, pentafluorobenzoyl- and 3,5-bis(trifluoromethyl)benzoyl-3Q were determined to be 15.9, 24.9, 22.8 and 22.1 min respectively, in stark contrast to the unmodified 3Q which provides a sharp peak with a retention time centered at ~ 13.5 min only at high concentrations (> 10 µg/mL or µg/g) while a broad peak (RT ~ 15–15.5 min) at low concentrations (< 5 µg/mL or µg/g). The developed protocol was used to derivatize 3Q in three separate matrices. The first two matrices were liquid samples featured during the 44th OPCW PT at two separate concentrations in each (5 and 50 µg/mL). The last matrix was a soil sample featured in the same 44th OPCW PT wherein the 3Q had been spiked at a 12 µg/g concentration. The approach involves the extraction of 3Q from all matrices followed by its acylation resulting in a second reportable analytical method for an OPCW PT. The presented derivatization strategies should find wide applicability particularly in laboratories involved with the analysis of this chemical weapon agent degradation product and those participating in the yearly OPCW PTs.

3-quinuclidinol↗

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers

Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT–TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H–C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties. Thermotropic liquid crystalline (LC) behavior is confirmed by cross-polarized optical microscopy (CPOM) and closely correlated with multiple thermal transitions observed by differential scanning calorimetry (DSC). This LC behavior allows us to develop and utilize a thermal annealing treatment that results in thin films with notable long-range order, as shown by grazing-incidence X-ray diffraction (GIXD). Specifically, we identified a first LC phase, ranging from 218 °C to 107 °C, as a nematic phase featuring preferential face-on π–π stacking and edge-on lamellar stacking exhibiting a large extent of disorder and broad orientation distribution. A second LC phase is observed from 107 °C to 48 °C, as a smectic A phase featuring sharp, highly ordered out-of-plane lamellar stacking features and sharp tilted backbone stacking peaks, while the structure of a third LC phase with a transition at 48 °C remains unclear, but resembles that of the solid state at ambient temperature. Furthermore, the significance of thermal annealing is evident in the ∼3-fold enhancement of the electrical conductivity of ferric tosylate-doped annealed films reaching 55 S cm −1 . More importantly, thermally annealed TPT–TT films exhibit both a narrow distribution of charge-carrier mobilities (1.4 ± 0.1) × 10 −2 cm 2 V −1 s −1 along with a remarkable device yield of 100% in an organic field-effect transistor (OFET) configuration. This molecular design approach to obtain highly ordered conjugated polymers in the solid state affords a deeper understanding of how intramolecular interactions and repeat-unit symmetry impact liquid crystallinity, solution aggregation, solution to solid-state transformation, solid-state morphology, and ultimately device applications.

Chemistry↗

Predissociation-based measurements of bond dissociation energies: US 2 , OUS, and USe

The uranium-containing molecules US 2 , OUS, and USe have been investigated using a pulsed laser ablation supersonic beam molecular source with time-of-flight mass spectrometric detection. Spectra have been recorded using the resonant two-photon ionization method over the spectroscopic range from 277 to 238 nm. These species have a myriad of excited electronic states in this spectroscopic region, leading to spectra that are highly congested and appear quasicontinuous. Sharp predissociation thresholds are observed, allowing precise bond dissociation energies to be measured. In the case of the triatomic molecules, it was necessary to use one laser for excitation and a delayed laser for ionization in order to observe a sharp predissociation threshold that allowed a precise bond dissociation energy to be measured. The resulting thermochemical values are D 0 (SU-S) = 4.910 ± 0.003 eV, D 0 (OU-S) = 5.035 ± 0.004 eV, and D 0 (USe) = 4.609 ± 0.009 eV. These results provide the first measurement of D 0 (USe) and reduce the error limits in the previous values of D 0 (SU-S) and D 0 (OU-S) by a factor of more than 70.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boosting H I -Galaxy Cross-Clustering Signal through Higher-Order Cross-Correlations

After reionization, neutral hydrogen (${\rm H\, \small {I}}$) traces the large-scale structure (LSS) of the Universe, enabling ${\rm H\, \small {I}}$ intensity mapping (IM) to capture the LSS in 3D and constrain key cosmological parameters. We present a new framework utilizing higher-order cross-correlations to study ${\rm H\, \small {I}}$ clustering around galaxies, tested using real-space data from the IllustrisTNG300 simulation. This approach computes the joint distributions of k-nearest neighbor (kNN) optical galaxies and the ${\rm H\, \small {I}}$ brightness temperature field smoothed at relevant scales (the kNN-field framework), providing sensitivity to all higher-order cross-correlations, unlike two-point statistics. To simulate ${\rm H\, \small {I}}$ data from actual surveys, we add random thermal noise and apply a simple foreground cleaning model, filtering out Fourier modes of the brightness temperature field with k ∥ < k min,∥ . Under current levels of thermal noise and foreground cleaning, typical of a Canadian Hydrogen Intensity Mapping Experiment (CHIME)-like survey, the ${\rm H\, \small {I}}$-galaxy cross-correlation signal in our simulations, using the kNN-field framework, is detectable at >30σ across r = [3, 12] h –1 Mpc. In contrast, the detectability of the standard two-point correlation function (2PCF) over the same scales depends strongly on the foreground filter: a sharp k ∥ filter can spuriously boost detection to 8σ due to position-space ringing, whereas a less sharp filter yields no detection. Nonetheless, we conclude that kNN-field cross-correlations are robustly detectable across a broad range of foreground filtering and thermal noise conditions, suggesting their potential for enhanced constraining power over 2PCFs.

79 ASTRONOMY AND ASTROPHYSICS↗

Cocoon shock breakout emission from binary neutron star mergers

Shock breakout emission is among the first observable signals in a wide variety of astrophysical phenomena, including neutron star (NS) mergers, and it can be the dominant component in low-luminosity short γ-ray bursts, as exemplified by GRB 170817A. In this work, we investigate the cocoon shock breakout emission in NS mergers and how its signal depends on the outermost layers of the ejecta profile, which we derive from general relativistic radiation hydrodynamic simulations. We study the formation of the cocoon as a consequence of a relativistic jet propagating through the ejecta. To explore the influence of the outermost layers of the ejecta on the breakout emission, we explore cases where the ejecta has a sharp cutoff or an extended smooth tail. We find that the shock breakout emission is strongly influenced by the shape of the ejecta outer layers, with extended tails yielding results consistent with the observed properties of GRB 170817A, whereas sharp cutoffs overestimate the radiated energy. Using a Bayesian analysis, we estimate the best fit parameters of the central engine, considering both accreting black hole and magnetized neutron star scenarios. Our findings indicate a slight preference for the scenarios where the engine is a black hole. Furthermore, our work probes the nature of neutron star mergers and highlights the importance of the shape of the ejecta profile in modeling early electromagnetic counterparts to these mergers.

79 ASTRONOMY AND ASTROPHYSICS↗

Nature of Excitons and Their Ligand-Mediated Delocalization in Nickel Dihalide Charge-Transfer Insulators

The fundamental optical excitations of correlated transition-metal compounds are typically identified with multielectronic transitions localized at the transition-metal site, such as d d transitions. In this vein, intense interest has surrounded the appearance of sharp, below-band-gap optical transitions, i.e., excitons, within the magnetic phase of correlated Ni 2 + van der Waals magnets. The interplay of magnetic and charge-transfer insulating ground states in Ni 2 + systems raises intriguing questions on the roles of long-range magnetic order and of metal-ligand charge transfer in the exciton nature, which inspired microscopic descriptions beyond typical d d excitations. Here we study the impact of charge transfer and magnetic order on the excitation spectrum of the nickel dihalides ( Ni X 2 , X = Cl , Br, and I) using Ni- L 3 edge resonant inelastic x-ray scattering (RIXS). In all compounds, we detect sharp excitations, analogous to the recently reported excitons, and assign them to spin-singlet multiplets of octahedrally coordinated Ni 2 + stabilized by intra-atomic Hund’s exchange. Additionally, we demonstrate that these excitons are dispersive using momentum-resolved RIXS. Our data evidence a ligand-mediated multiplet dispersion, which is tuned by the charge-transfer gap and independent of the presence of long-range magnetic order. This reveals the mechanisms governing nonlocal interactions of on-site d d excitations with the surrounding crystal or magnetic structure, in analogy to ground-state superexchange. These measurements thus establish the roles of magnetic order, self-doped ligand holes, and intersite-coupling mechanisms for the properties of d d excitations in charge-transfer insulators. Published by the American Physical Society 2024

2-dimensional systems↗

Magnetoelastic-coupling-assisted first-order antiferromagnetic transitions in the corrugated honeycomb-lattice compounds (Ca, Sr) ⁢Mn 2 ⁢ P 2

Understanding the origin of unconventional magnetic order is a central theme in the research field of functional quantum materials for spin-dependent applications. In general, a paramagnetic (PM) to antiferromagnetic (AFM) transition is of thermodynamically second order in nature in the absence of a magnetic field. In the magnetically frustrated corrugated-honeycomb lattice compounds (Ca, Sr) ⁢Mn 2 ⁢ P 2 , electrical resistivity 𝜌 measurements in the 𝑎⁢𝑏 plane are reported to exhibit sharp discontinuities at the respective PM to AFM ordering temperatures 𝑇 N = 69.5 and 53 K, respectively, signifying the unusual first-order nature of the AFM transition. To reveal the origin of such anomalous transitions, high-resolution linear thermal-expansion measurements are reported for both CaMn 2 ⁢P 2 and SrMn 2 ⁢ P 2 in the 𝑎⁢𝑏 plane and along the 𝑐 axis using capacitance dilatometry. The thermal expansion measurements show a sharp discontinuity in Δ⁢𝐿/𝐿 at 𝑇 N , yielding a diverging behavior in the thermal expansion coefficient 𝛼⁡(𝑇) associated with strong magnetoelastic coupling, driving the first-order AFM transition in CaMn 2 ⁢P 2 . However, this effect is weaker in SrMn 2 ⁢P 2 , consistent with the magnetic entropy changes 𝑆⁡(𝑇) obtained from the heat-capacity measurements. Temperature-dependent 𝑎⁢𝑏-plane x-ray diffraction measurements for CaMn 2 ⁢ P 2 near its 𝑇 N yield a volume thermal expansion coefficient consistent with literature data for other materials. The uniaxial pressure derivatives of 𝑇 N in the two compounds are found to be respectively opposite in sign, presumably due to the different magnetic structures.

Pakhira, Santanu [Maulana Azad National Institute ↗

Scatter and Blur Corrections for High-Energy X-Ray Radiography

High-energy X-ray radiography is useful as a highly penetrating method for imaging through dense materials. However, the primary modes of interaction of X-rays at these energies involve scattering or the production of secondary high-energy photons, which can interfere with the image. In addition, detector blurring, often resulting from scatter within the detector, can reduce image sharpness. Both of these processes can be mitigated with the use of convolution kernels, with the main challenge being that the proper kernel to use is not known, particularly for the scatter contribution. By radiographing solid slabs of uniform attenuation, we show that point spread functions and material-specific point scatter functions can be determined to significantly reduce the effect of detector blurring and object scatter. Constraining the fits to the slabs and uniform transmission within the slabs is sufficient to recover these functions. A functional form that reproduces the angular distribution of high-energy bremsstrahlung X-rays is presented for recovering point scatter functions. In conclusion, the method is applied to radiographs of objects from bremsstrahlung X-ray sources operating at 4- and 7.5-MV endpoint energies and a significant increase in sharpness is observed.

Blind deconvolution↗

Unzipping hBN with ultrashort mid-infrared pulses

Manipulating the nanostructure of materials is critical for numerous applications in electronics, magnetics, and photonics. However, conventional methods such as lithography and laser writing require cleanroom facilities or leave residue. We describe an approach to creating atomically sharp line defects in hexagonal boron nitride (hBN) at room temperature by direct optical phonon excitation with a mid-infrared pulsed laser from free space. We term this phenomenon “unzipping” to describe the rapid formation and growth of a crack tens of nanometers wide from a point within the laser-driven region. Formation of these features is attributed to the large atomic displacement and high local bond strain produced by strongly driving the crystal at a natural resonance. This process occurs only via coherent phonon excitation and is highly sensitive to the relative orientation of the crystal axes and the laser polarization. Its cleanliness, directionality, and sharpness enable applications such as polariton cavities, phonon-wave coupling, and in situ flake cleaving.

36 MATERIALS SCIENCE↗

Nonseeded linewise temperature measurements by resonantly ionized photoemission thermometry in a Mach 4 Ludwieg tube

A one-dimensional (1D) thermometry using oxygen-tagging resonantly ionized photoelectron thermometry (O 2 RIPT) was employed to investigate thermal gradients within a Mach 4 Ludwieg tube. The Ludwieg tube is pulsed with a test duration of approximately 100 ms, providing a cold supersonic flow at Mach 4 ideal for studying aerothermal effects. This study focused on measuring freestream temperatures, capturing shock-induced heating behind a detached bow shock from a blunt cylinder, and resolving sharp temperature variations across a bow shock generated by a cylinder. The O 2 RIPT technique produced strong emission signals extending approximately 4 cm long, demonstrating its capability for precise temperature measurements in high-speed wind tunnel environments. The results confirm that O 2 RIPT is well-suited for applications in large-scale aerodynamic testing facilities, particularly in regions with strong compression effects, enabling the resolution of sharp thermal gradients. This method presents a promising solution for thermometry in dynamic flow conditions relevant to various experimental ground-test facilities.

McCord, Walker (ORCID:0000000179747550)↗

Microscopy X-ray imaging enriched with small angle X-ray scattering for few nanometer resolution reveals shock waves and compression in intense short pulse laser irradiation of solids

Understanding how laser pulses compress solids into high-energy-density states requires diagnostics that simultaneously resolve macroscopic geometry and nanometer-scale structure. Here we present a combined X-ray imaging (XRM) and small-angle X-ray scattering (SAXS) approach that bridges this diagnostic gap. Using the Matter in Extreme Conditions end station at LCLS, we irradiated 25 μm copper wires with 45 fs, 0.9 J, 800 nm pulses at 3.5 × 10 19 W/cm 2 while probing with 8.2 keV XFEL pulses. XRM visualizes the evolution of ablation, compression, and inward-propagating fronts with ∼ 200 nm resolution, while SAXS quantifies their nanometer-scale sharpness via the time-resolved evolution of scattering streaks. The joint analysis reveals that an initially smooth compression steepens into a nanometer-sharp shock front after t sh ≈ (18 ± 3) ps, consistent with an analytical steepening model and hydrodynamic simulations. The front reaches a velocity of c sh ≈ 25 k m / s and a lateral width of several tens of microns, demonstrating direct observation of shock formation and decay at solid density for the first time with few-nanometer precision. This integrated XRM–SAXS method establishes a quantitative, multi-scale diagnostic of laser-driven shocks in dense plasmas relevant to inertial confinement fusion, warm dense matter, and planetary physics.

Kluge, Thomas [Helmholtz-Zentrum Dresden-Rossendor↗

Impacts of spatial heterogeneity of anthropogenic aerosol emissions in a regionally refined global aerosol–climate model

Abstract. Emissions of anthropogenic aerosol and their precursors are often prescribed in global aerosol models. Most of these emissions are spatially heterogeneous at model grid scales. When remapped from low-resolution data, the spatial heterogeneity in emissions can be lost, leading to large errors in the simulation. It can also cause the conservation problem if non-conservative remapping is used. The default anthropogenic emission treatment in the Energy Exascale Earth System Model (E3SM) is subject to both problems. In this study, we introduce a revised emission treatment for the E3SM Atmosphere Model (EAM) that ensures conservation of mass fluxes and preserves the original emission heterogeneity at the model-resolved grid scale. We assess the error estimates associated with the default emission treatment and the impact of improved heterogeneity and mass conservation in both globally uniform standard-resolution (∼ 165 km) and regionally refined high-resolution (∼ 42 km) simulations. The default treatment incurs significant errors near the surface, particularly over sharp emission gradient zones. Much larger errors are observed in high-resolution simulations. It substantially underestimates the aerosol burden, surface concentration, and aerosol sources over highly polluted regions, while it overestimates these quantities over less-polluted adjacent areas. Large errors can persist at higher elevation for daily mean estimates, which can affect aerosol extinction profiles and aerosol optical depth (AOD). We find that the revised treatment significantly improves the accuracy of the aerosol emissions from surface and elevated sources near sharp spatial gradient regions, with significant improvement in the spatial heterogeneity and variability of simulated surface concentration in high-resolution simulations. In the next-generation E3SM running at convection-permitting scales where the resolved spatial heterogeneity is significantly increased, the revised emission treatment is expected to better represent the aerosol emissions as well as their lifecycle and impacts on climate.

54 ENVIRONMENTAL SCIENCES↗

Beyond pinball loss: Quantile methods for calibrated uncertainty quantification

Amongthemanywaysofquantifying uncertainty in a regression setting, specifying the full quantile function is attractive, as quantiles are amenable to interpretation and evaluation. A model that predicts the true conditional quantiles for each input, at all quantile levels, presents a correct and efficient representation of the underlying uncertainty. To achieve this, many current quantile-based methods focus on optimizing the pinball loss. However, this loss restricts the scope of applicable regression models, limits the ability to target many desirable properties (e.g. calibration, sharpness, centered intervals), and may produce poor conditional quantiles. In this work, we develop new quantile methods that address these shortcomings. In particular, we propose methods that can apply to any class of regression model, select an explicit balance between calibration and sharpness, optimize for calibration of centered intervals, and produce more accurate conditional quantiles. We provide a thorough experimental evaluation of our methods, which includes a high dimensional uncertainty quantification task in nuclear fusion.

97 MATHEMATICS AND COMPUTING↗

An Investigation of the Effects of Nose and Lip Shapes for an Underslung Scoop Inlet at Mach Numbers from 0 to 1.9

An experimental investigation was conducted to determine the performance characteristics an underslung nose-scoop air-induction system for a supersonic airplane. Five different nose shapes, three lip shapes, and two internal diffusers were investigated. Tests were made at Mach numbers from 0 to 1.9, angles of attack from 0 deg to approximately l5 deg, and mass-flow ratios from 0 to maximum obtainable. It was found that the underslung nose-scoop inlet was able to operate at Mach numbers from 0.6 to 1.9 over a large positive angle-of-attack range without adverse effects on the pressure recovery. Although there was no one inlet configuration that was markedly superior over the entire range of operating variables, the arrangement having a nose designed to give increased supersonic compression at low angles of attack, and a sharp lip (configuration designated N3L3) showed the most favorable performance characteristics over the supersonic Mach number range. Inlets with sizable lip radii gave satisfactory performance up to a Mach number of 1.5; however, as a result of an increase in drag, the performance of such inlets was markedly inferior to the sharp-lip configuration above Mach numbers of 1.5. Throughout the range of test Mach numbers all inlet configurations evidenced stable air-flow characteristics over the mass-flow range for normal engine operation. Analysis of the inlet performance on the basis of a propulsive thrust parameter showed that a fixed inlet area could be used for Mach numbers up to 1.5 with only a small sacrifice in performance.

NOSE CONE↗

Drag of a Supercritical Body of Revolution in Free Flight at Transonic Speeds and Comparison with Wind Tunnel Data

The forebody drag of a supercritical body of revolution was measured in free flight over a Mach number range of 0.85 to 1.05 and a Reynolds number range of 11.5 x 10 to the 6th power to 19.4 x 10 to the 6th power and was compared with wind-tunnel data. The forebody drag coefficient for a Mach number less than 0.96 was 0.111 compared with the wind-tunnel value of 0.103. A gradual increase in the drag occurred in the Langley 8-foot transonic pressure tunnel at a lower Mach number than in the Langley 16-foot transonic tunnel or in the free-flight test. The sharp drag rise occurred near Mach 0.98 in free flight whereas the rise occurred near Mach 0.99 in the Langley 16-foot transonic tunnel. The sharp rise was not as pronounced in the Langley 8-foot transonic pressure tunnel and was probably affected by tunnel-wall-interference effects. The increase occurred more slowly and at a higher Mach number. These results indicate that the drag measurements made in the wind tunnels near Mach 1 were significantly affected by the relative size of the model and the wind tunnel.

Usry, J. W.↗

Effect of trailing edge geometry and thickness on the performance of certain turbine stator blading

The experimental and analytical investigation included solid blades with five different trailing-edge thicknesses and four different trailing-edge geometries. One of the geometries was round, one was square, one was tapered from the suction surface, and the other tapered from the pressure surface. One of the trailing-edge thicknesses was sharp edged; the other four thicknesses were equivalent to about 5, 11, 16, and 20 percent of the blade throat width. The experimental results show increased efficiency loss for increased trailing-edge thickness for all trailing-edge geometries. The blade with round trailing edge, equal to about 11 percent of the blade throat width, had 60 percent more loss than the sharp-edged blade. For the same trailing-edge thickness, square trailing edges caused more loss than round trailing edges, and the tapered trailing edges caused about the same loss as the round trailing edges.

Prust, H. W., Jr.↗

The relative age of the transition zone between Hellas and the Martian cratered terrain.

Consideration of the relationships of craters to scarps and ridges and of the antiquity of Hellas relative to the cratered terrain. Scarps and ridges in the transition zone between Hellas and the cratered terrain both postdate and predate large craters. It appears that there are a number of craters which are older than the transition zone structures, which in turn are presumably related in some way to the formation of Hellas. Sharp et al. (1971) have suggested impact, large-scale volcanic explosion, or subsidence for the origin of Hellas. Volcanic explosion seems the least likely explanation, for the resulting deficiency of mass beneath Hellas should induce later isostatic rebound, contrary to observations of the transition zone which imply subsidence relatively late in the history of the Martian surface. An origin of Hellas by impact with later isostatic subsidence (because of a dense mass under its floor, as suggested by Sharp et al.) to account for the characteristics of the transition zone seems to be the best model, and may also account for the featureless floor of the basin.

Thorman, C. H.↗

Structure of molybdenum disulfide films sputtered on substrates at various temperatures

Molybdenum disulfide films 300 to 400 A thick were rf sputtered on aluminum and nickel surfaces at elevated, ambient, and liquid nitrogen temperatures. Electron transmission micrographs and electron diffraction patterns were taken to determine the structural growth. These transmission micrographs revealed that sputtered MoS2 films at ambient and elevated temperatures (320 and 150 C) formed an irregular network of ridges. The electron diffraction patterns of these films showed relatively sharp diffraction rings, indicating crystallinity. The transmission micrographs of sputtered films at liquid nitrogen temperatures revealed a continuous featureless film. The electron diffraction patterns showed broad, diffused rings indicating an amorphous film. The transmission micrographs of a post-annealed (425 C) MoS2 film sputtered at liquid-nitrogen temperature revealed the tendency for ridge formation. Electron diffraction patterns also showed increased sharpness of the diffraction rings. Friction tests showed that MoS2 films deposited at ambient and elevated temperatures exhibited good lubricating properties. The MoS2 films deposited at cryogenic temperatures had no lubricating characteristics.

Spalvins, T.↗