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At least 289 records · Page 16

Reimagining the $e_g$ 1 Electronic State in Oxygen Evolution Catalysis: Oxidation-State-Modulated Superlattices as a New Type of Heterostructure for Maximizing Catalysis

We report that the discovery of solid-phase, inexpensive transition-metal-based water oxidation catalysts is a central goal for renewable energy, and has led to a general consensus that a partially populated metal e g d-electronic state is desirable, leading to favorable catalysis for certain elements in specific oxidation states. In manganese systems, the key species is manganese(III), whose high-spin d 4 electronic configuration places an unpaired electron in the e g orbital, which is postulated to contribute to electronic and structural features that support catalysis. Based on density functional theory calculations, it is predicted that electron transfer would be facilitated by a catalyst with alternating low- and high-Mn III -content sheets, which positions neighboring band edges in closer energetic proximity. The preparation of such catalysts is demonstrated for the first time and it is shown that the catalytic activity is maximized in these systems over more uniform, but more Mn III -rich systems. The best catalyst possesses alternating high-and low-average oxidation state sheets with interlayer Cs + ions, and has an overpotential of 450 mV at 10 mA, which represents an improvement of 250 mV over the best unmodified synthetic potassium birnessites. Using scanning tunneling spectroscopy, bandgap modulations consistent with the theoretically predicted band edge shifts are detected.

36 MATERIALS SCIENCE↗

T-1065: Secondary Emitters Study

One possibility to make a fast and radiation resistant shower maximum (SM) detector or preshower detector is to use a secondary emitter (SE) as an active element. This method was proposed in 1990. Micro channel plates (MCP) were used as SE in the SM. The attractive properties of such SM are: 1) a two-dimensional map of energy at the SE location; 2) timing information at few tens of picosecond level, also as transverse shower size and 3) possible separation of electromagnetic and hadronic energy based on the differences of the shower size and timing. An electron-multiplier-based sampling calorimeter requires thin planar detectors at an affordable cost. Large-area photo detectors based on ALD-functionalized 20-cm-square borosilicate glass capillary micro-channel plates (MCPs), currently being developed by the LAPPD Collaboration, are candidates for the active elements. The first results of the new shower maximum detector with the micro channel plate photomultiplier (MCP-PMT) as active elements are described. The current proposal is the next natural step in this direction. The experimenters propose using large-area MCPs assembled without the usual bialkali photocathodes as the active element in sampling calorimeters. LAPPD modules without photocathodes can be economically assembled in a glove box and then pumped and sealed using the process to construct photomultipliers, bypassing the slow and expensive vacuum-transfer process required by bialkali photocathodes. The first use of electron multipliers, in this case MCPs (Fig. 1, left) as an active element in multi-layer sampling calorimeters is described. A chevron of two MCPs in vacuum, was located behind a tungsten plate on which 5 GeV and 26 GeV electrons were incident (Fig. 1, right). The amplitude of the MCP signal (Fig. 2) as a function of the tungsten thickness was measured. The primary electrons produce a shower of secondary particles, including positron-electron pairs and gammas; the response of the MCPs (Fig. 2, left) is proportional to the number of particles in the shower, which is dependent on the initial particle energy. The MCP signal shape is presented in the Fig. 2, right). The FWHM of the signal is 1 ns.

43 PARTICLE ACCELERATORS↗

Metallopolymerization as a Strategy to Translate Ligand-Modulated Chemoselectivity to Porous Catalysts

Porous catalysts have garnered substantial interest as potential platforms for group-transfer catalysis due to the ability to noncovalently colocalize substrates in proximity to site-isolated reactive intermediates. In contrast to soluble molecular catalysts, the limited synthetic toolbox available to prepare porous catalysts presents a formidable challenge to controlling the primary coordination sphere of lattice-confined catalysts and thus modulating the electronic structures of reactive catalyst intermediates. Here, we utilize Sonogashira cross-coupling chemistry to prepare a family of porous metallopolymers in the primary coordination sphere of Ru 2 sites. The newly synthesized materials are characterized by IR, elemental analysis, gas sorption, powder X-ray diffraction, thermogravimetric analysis, X-ray absorption spectroscopy, and diffuse-reflectance UV–vis-NIR spectroscopy. The resulting porous materials are catalysts for nitrene-transfer chemistry, and the chemoselectivity for allylic amination versus olefin aziridination can be tuned by modulating the primary coordination sphere of the catalyst sites. Furthermore, the demonstration of metallopolymerization as a rational synthetic strategy enables ligand-modulated chemoselectivity to be achieved with porous catalysts and represents a new opportunity to tailor the functionality of heterogeneous catalyst materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic doping of transition metal oxide perovskites

CaFeO{sub 3} is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO{sub 3}. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

HPC Institutional Computing Project: W15_lesreactiveflow KIVA-hpFE Development: A Robust and Accurate Engine Modeling Software

KIVA-hpFE is a high performance computer software for solving the physics of multi-species and multiphase turbulent reactive flow in complex geometries having immersed moving parts. The code is written in Fortran 90/95 and can be used on any computer platform with any popular complier. The code is in two versions, a serial version and a parallel version utilizing MPICH2 type Message Passing Interface (MPI or Intel MPI) for solving distributed domains. The parallel version is at least 30x faster than the serial version and much faster than our previous generation of parallel engine modeling software, by many factors. The 5th generation algorithm construction is a Galerkin type Finite Element Method (FEM) solving conservative momentum, species, and energy transport equations along with two-equation turbulent model k-ω Reynolds Averaged Navier-Stokes (RANS) model and a Vreman type dynamic Large Eddy Simulation (LES) method. The LES method is capable modeling transitional flow from laminar to fully turbulent; therefore, this LES method does not require special hybrid or blending to walls. The FEM projection method also uses a Petrov-Galerkin (P-G) stabilization along with pressure stabilization. We employ hierarchical basis sets, constructed on the fly with enrichment in areas associated with relatively larger error as determined by error estimation methods. In addition, when not using the hp-adaptive module, the code employs Lagrangian basis or shape functions. The shape functions are constructed for hexahedral, prismatic and tetrahedral elements. The software is designed to solve many types of reactive flow problems, from burners to internal combustion engines and turbines. In addition, the formulation allows for direct integration of solid bodies (conjugate heat transfer), as in heat transfer through housings, parts, cylinders. It can also easily be extended to stress modeling of solids, used in fluid structure interactions problems, solidification, porous media modeling and magneto hydrodynamics.

97 MATHEMATICS AND COMPUTING↗

pH-Dependent Vibrational Dynamics Drives Excited-State Quenching in the Phycobiliprotein Complex PC645

Phycocyanin 645 (PC645) is a closed-form lightharvesting complex found in the lumen of the photosynthetic membrane of cryptophyte algae. These peripheral antenna complexes contain bilin chromophores that absorb sunlight and transfer excitation energy to the core antenna complexes embedded in the thylakoid membrane. The location of cryptophyte antenna complex on the luminal side of the membrane is unusual. During photosynthetic activity, the pH of the lumen drops, by up to two pH units. There is little known about how this pH-change affects the light-harvesting complexes. In this study, we report multiscale simulations using a computationally efficient density functional tight-binding framework to investigate the spectroscopy and excitation energy transfer in the PC645 complex. Complementary experiments were conducted using both steady-state and time-resolved spectroscopic measurements at low, neutral, and high pH values. Our study shows that (de)protonation of specific bilin pigments, namely, the mesobiliverdins (MBVs), modulates the excitation energies, excitonic couplings, and spectral densities. These changes cause excitation transfer rates to increase by up to a factor of two to three, leading to pH-dependent energy transfer pathways in the complex. Using this model, we calculated the pH-dependent fluorescence quantum yield of the system, obtaining quantitative agreement with the experimental results. These computational simulations, supported by experiments, identify MBVs as a more prominent excitation sink than previously realized, and that this role is tuned by pH.

Maity, Sayan [Constructor Univ., Bremen (Germany);↗

Structural and Functional Characterization of a Single-chain Peptide-MHC Molecule that Modulates both Naive and Activated CD8plus T Cells

Peptide-MHC (pMHC) multimers, in addition to being tools for tracking and quantifying antigen-specific T cells, can mediate downstream signaling after T-cell receptor engagement. In the absence of costimulation, this can lead to anergy or apoptosis of cognate T cells, a property that could be exploited in the setting of autoimmune disease. Most studies with class I pMHC multimers used noncovalently linked peptides, which can allow unwanted CD8{sup +} T-cell activation as a result of peptide transfer to cellular MHC molecules. To circumvent this problem, and given the role of self-reactive CD8{sup +} T cells in the development of type 1 diabetes, we designed a single-chain pMHC complex (scK{sup d}.IGRP) by using the class I MHC molecule H-2K{sup d} and a covalently linked peptide derived from islet-specific glucose-6-phosphatase catalytic subunit-related protein (IGRP{sub 206-214}), a well established autoantigen in NOD mice. X-ray diffraction studies revealed that the peptide is presented in the groove of the MHC molecule in canonical fashion, and it was also demonstrated that scK{sup d}.IGRP tetramers bound specifically to cognate CD8{sup +} T cells. Tetramer binding induced death of naive T cells and in vitro- and in vivo-differentiated cytotoxic T lymphocytes, and tetramer-treated cytotoxic T lymphocytes showed a diminished IFN-{gamma} response to antigen stimulation. Tetramer accessibility to disease-relevant T cells in vivo was also demonstrated. Our study suggests the potential of single-chain pMHC tetramers as possible therapeutic agents in autoimmune disease. Their ability to affect the fate of naive and activated CD8{sup +} T cells makes them a potential intervention strategy in early and late stages of disease.

59 BASIC BIOLOGICAL SCIENCES↗

Major improvements on the longwave radiative interactions between surface and clouds in the polar regions in atmospheric global circulation model

Motivations: One of the most important tasks in the study of physical and socioeconomic aspects of climate change is the simulation of polar climate and how it changes in response to global warming. One import component of the polar energy budget (and thus of polar climate) is the radiative interaction between surface and clouds. As of today, the vast majority of state-of-the-art global climate models (GCMs), including all three US flagship GCMs (NCAR CESM, GFDL CM3, and GISS E2-H/E2-R), still assume constant surface emissivity overall spectral bands in their longwave radiation treatment. Similarly, a majority of state-of-the-art GCMs assume non-scattering clouds in the longwave spectrum, including both the NCAR CESM and GFDL CM3. The issues of ignoring spectral variation in surface emissivity and scattering by clouds manifest themselves in the far-infrared (IR) over the polar continents because (1) there is so little water vapor in such areas that surface far-IR emission can reach clouds; and (2) the imaginary part of the refractive index of ice has a local minimum over 350-550 cm-1, which implies possible strong scattering effects over this spectral region both within and between the snow surface and ice clouds. Our sensitivity studies using CloudSat-retrieved hydrometeor profiles over the high-elevation Antarctic continent show that, in winter, an appropriate inclusion of snow surface spectral emissivity and ice cloud scattering in radiative transfer calculations can noticeably reduce the monthly-mean surface net downward far-IR flux and net atmospheric far-IR emission over the entire region. For the far-IR alone, the magnitude of these effects is ~1Wm-2 or even larger. Projection Objectives: We propose to carry out the following studies: (1) Develop or update schemes that can be used in the CESM to compute the optical properties of the snow surface and ice clouds consistently across the longwave and the shortwave spectrum; (2) Modify the longwave radiation scheme in the CESM such that it can incorporate surface spectral emissivity and scattering of clouds; (3) Validate schemes developed for (1) and (2) against measurements or benchmark models; (4) Evaluate the effects of these new treatments on the simulated polar energy budget and climate by the CESM. Technical Approaches:1.Use a detailed snowpack radiative transfer model to simulate spectrally resolved emissivity of snow surfaces as a function of snow effective radius. The model will be validated against available high spectral-resolution measurements of snow spectral emissivity (ASTER spectra library v2.0). Currently the CESM prognoses vertically-resolved snow effective radius, and snow shortwave albedo is parameterized based on snow effective radius. Our treatment of snow spectral emissivity here will be consistent with the treatment of snow albedo in the shortwave and seamlessly connected with the snow physical module in the CESM. 2. Update the parameterization of ice cloud optical properties in the CESM, for both longwave and shortwave, based on the latest ice-cloud scattering database developed by co-I Prof. Yang. 3. Modify RRTMG_LW, the current longwave radiation scheme in the CESM, to include the surface spectral emissivity and the scattering of clouds in the longwave calculation. Validate modified scheme against a line-by-line radiative transfer model with multiple scattering capability (LBLRTM/CHARTS). 4. Implement products from Steps 1-3 into the CESM and conduct simulations to evaluate their effects on the simulated polar climate and energy budget. These runs will be compared to control runs and evaluated using routine model-observation diagnostics, including data from the ARM NSA (North Slope of Alaska) site. Moreover, a novel aspect in this step is that we will evaluate the simulated longwave band-by-band fluxes and cloud radiative effect against observational counterparts over both polar continents, using a product recently derived by the lead PI Prof. Huang from collocated AIRS and CERES satellite observations from 2002 to 2013. Benefits and outcomes: This project will significantly improve the longwave radiation scheme in the CESM and its successors and provide more realistic treatment of radiative interactions between polar surfaces and clouds. In the future, it will also be straightforward to extend this framework to include spectral emissivity of all surface types. This is responsive to identified DoE Earth System Modeling Science Drivers to improve the performance of the fully coupled climate system modeling and to help address questions on how rapid changes in cryospheric systems interact with the climate system.

54 ENVIRONMENTAL SCIENCES↗

Coverage dependent work function of graphene on a Cu(111) substrate with intercalated alkali metals

Using first-principles calculations, it is shown that the work function of graphene on copper can be adjusted by varying the concentration of intercalated alkali metals. Using density functional theory, we calculate the modulation of work function when Li, Na, or K are intercalated between graphene and a Cu(111) surface. Furthermore, the physical origins of the change in work function are explained in terms of phenomenological models accounting for the formation and depolarization of interfacial dipoles and the shift in the Fermi-level induced via charge transfer.

36 MATERIALS SCIENCE↗

Refining NEAMS MARVEL Reactor Model Accuracy

This report outlines the progress of Idaho National Laboratory (INL) in improving the fidelity of the multiphysics model of the Microreactor Applications Research Validation and Evaluation (MARVEL) reactor developed in FY24. The multiphysics model firstly developed in FY24 leverages three single-physics models coupled via the MOOSE’s MultiApps and Transfer systems. The first single-physics model, that functions as the driver application, leverages Griffin to model the neutron transport in the core through the discontinuous finite element (DFEM) discrete ordinates solver (SN). The second single-physics model uses BISON to compute the solid temperature in the reactor. Finally, the System Analysis Module (SAM) was used to model the flow of the sodium-potassium eutectic in the primary loop. In this report we detail the following improvement and enhancements: • An updated mesh leveraging the latest feature in the reactor module (see Section 3.1.).

42 - ENGINEERING↗

The role of Tyr34 in proton coupled electron transfer and product inhibition of manganese superoxide dismutase

Human manganese superoxide dismutase (MnSOD) plays a crucial role in controlling levels of reactive oxygen species (ROS) by converting superoxide (O$^{•–}_{2}$) to molecular oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) with proton-coupled electron transfers (PCETs). A key catalytic residue, Tyr34, determines the activity of human MnSOD and also becomes post-translationally inactivated by nitration in various diseases associated with mitochondrial dysfunction. Tyr34 has an unusual pK a due to its proximity to the Mn metal and undergoes cyclic deprotonation and protonation events to promote the electron transfers of MnSOD. Neutron diffraction, X-ray spectroscopy, and quantum chemistry calculations in oxidized, reduced and product inhibited enzymatic states shed light on the role of Tyr34 in MnSOD catalysis. The data identify the contributions of Tyr34 in MnSOD activity that support mitochondrial function and give a thorough characterization of how a single tyrosine modulates PCET catalysis. Product inhibition occurs by an associative displacement mechanism.

60 APPLIED LIFE SCIENCES↗

Engineering a highly dispersed core@shell structure for efficient photocatalysis: A case study of ternary novel BiOI@MIL-88A(Fe)@g-C3N4 nanocomposite

Highlights: • Novel ternary BiOI@MIL-88A(Fe)@g-C{sub 3}N{sub 4} core@shell photocatalyst is reported. • Photocatalytic degradation mechanism of organic pollutants is investigated. • It is divulged that the photodegradation is increased by BiOI supporting. • Core@shell structure of MIL-88A(Fe)@g-C{sub 3}N{sub 4} causes high activity. • Strong visible light absorption and electron transfer improve activity. - Abstract: Ternary novel BiOI@MIL-88A(Fe)@g-C{sub 3}N{sub 4} nanocomposite with core@shell structure was successfully synthesized by hydrothermal method. Fabricated photocatalysts were characterized and results confirmed the formation of MIL-88A(Fe)@g-C{sub 3}N{sub 4} core@shell structure and subsequently BiOI decoration on the surface of MIL-88A(Fe)@g-C{sub 3}N{sub 4}. Photocatalytic performances of prepared samples were investigated for degradation of Acid Blue 92 (AB92), Rhodamine B (RhB) and phenol under visible irradiation. It is clearly demonstrated that the as-prepared ternary BiOI@MIL-88A(Fe)@g-C{sub 3}N{sub 4} composites exhibits exceptional visible-light photocatalytic activities for cationic, anionic as well as neutral pollutant molecules compared to the widely accepted outstanding g-C{sub 3}N{sub 4}. It is mainly proved that the exceptional photocatalytic efficiencies are comprehensively ascribed to the porous structure of MIL-88A(Fe)@g-C{sub 3}N{sub 4}, greatly promoted charge separation and introduced catalytic functions to the carrier-related redox reactions by decorating BiOI and coupling g-C{sub 3}N{sub 4}, to modulate holes and electrons. Additionally, studies performed using radical scavengers showed the main reactive species in the photocataytic reaction for all chemical pollutant degradation.

36 MATERIALS SCIENCE↗

A Strategy for Forced Oscillation Suppression

Wide-area time-synchronized measurements have recently revealed troublesome forced oscillations (FOs) within modern synchronized power grids. In some cases, these FOs represent a dangerous hazard to the system. Recent research has focused on locating the source of FOs to provide operators with knowledge for mitigating their impact locally. This paper presents a complementary mitigation strategy, which is to purposely induce a second oscillation into the grid which cancels the impact of the FO. Such a strategy is complementary in that it may provide valuable time to operators attempting to locate the FOs source and to determine how to rectify it. This paper presents a suppression control strategy which modulates controllable devices to automatically cancel the impact of the FO without the need for locating the source of the original FO. The strategy is based upon tuned feedback control. In this study, the approach is demonstrated on a simulation system via modulation of inverter-based generation.

42 ENGINEERING↗

A Versatile Integrated Ambient Ionization Source Platform

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Changing Directions: Influence of Ligand Electronics on the Directionality and Kinetics of Photoinduced Charge Transfer in Cu(I)Diimine Complexes

A key challenge to the effective utilization of solar energy is to promote efficient photoinduced charge transfer, specifically avoiding unproductive, circuitous electron-transfer pathways and optimizing the kinetics of charge separation and recombination. We hypothesize that one way to address this challenge is to develop a fundamental understanding of how to initiate and control directional photoinduced charge transfer, particularly for earth-abundant first-row transition-metal coordination complexes, which typically suffer from relatively short excited-state lifetimes. Here, in this paper, we report a series of functionalized heteroleptic copper(I)bis(phenanthroline) complexes, which have allowed us to investigate the directionality of intramolecular photoinduced metal-to-ligand charge transfer (MLCT) as a function of the substituent Hammett parameter. Ultrafast transient absorption suggests a complicated interplay of MLCT localization and solvent interaction with the Cu(II) center of the MLCT state. This work provides a set of design principles for directional charge transfer in earth-abundant complexes and can be used to efficiently design pathways for connecting the molecular modules to catalysts or electrodes and integration into systems for light-driven catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid RNA-ligand interaction analysis through high-information content conformational and stability landscapes

The structure and biological properties of RNAs are a function of changing cellular conditions, but comprehensive, simultaneous investigation of the effect of multiple interacting environmental variables is not easily achieved. We have developed an efficient, high-throughput method to characterize RNA structure and thermodynamic stability as a function of multiplexed solution conditions using Förster resonance energy transfer (FRET). In a single FRET experiment using conventional quantitative PCR instrumentation, 19,400 conditions of MgCl 2 , ligand and temperature are analysed to generate detailed empirical conformational and stability landscapes of the cyclic diguanylate (c-di-GMP) riboswitch. This method allows rapid comparison of RNA structure modulation by cognate and non-cognate ligands. Landscape analysis reveals that kanamycin B stabilizes a non-native, idiosyncratic conformation of the riboswitch that inhibits c-di-GMP binding. Our research demonstrates that allosteric control of folding, rather than direct competition with cognate effectors, is a viable approach for pharmacologically targeting riboswitches and other structured RNA molecules.

biological sciences↗

Late Metal Sandwich Catalysts for Olefin Polymerization

Polyolefins are by far the most ubiquitous industrially produced polymers and are primarily produced by early transition metal catalysts. These catalysts are not functional group tolerant, and copolymerization of ethylene and polar vinyl monomers is quite challenging. Furthermore, early metal catalysts convert ethylene to linear polyethylene, and introduction of branches requires addition of comonomers. In this Account, we describe our efforts in designing and implementing new Pd(II) and Ni(II) olefin polymerization catalysts based on mechanistic understanding of the chain growth process. Here, the original hindered nickel- and palladium-aryl-substituted diimine complexes were discovered in 1995. The key to the success of these now “classic” systems in generating high polymers rather than dimers or oligomers was realizing that incorporation of ortho-disubstituted aryl groups partially blocks the axial sites of the metal and thus retards the rate of chain transfer relative to propagation. Two key features of these late metal catalysts distinguish them from early metal complexes. First, they tolerate certain functional groups, which allows copolymerization of olefins with polar comonomers. Second, they can form a branched polymer from ethylene without the need to add α-olefin comonomers. Importantly, for nickel catalysts, branching levels can be modulated by changing reaction conditions, such as temperature and monomer pressure.

Catalysts↗

Neural coding using telegraphic switching of magnetic tunnel junction

In this work, we present a synaptic transmission representing neural coding with spike trains by using a magnetic tunnel junction (MTJ). Telegraphic switching generates an artificial neural signal with both the applied magnetic field and the spin-transfer torque that act as conflicting inputs for modulating the number of spikes in spike trains. The spiking probability is observed to be weighted with modulation between 27.6% and 99.8% by varying the amplitude of the voltage input or the external magnetic field. With a combination of the reverse coding scheme and the synaptic characteristic of MTJ, an artificial function for the synaptic transmission is achieved.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗