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At least 163 records · Page 9

Surface contamination analysis technology team overview

A team was established which consisted of representatives from NASA (Marshall Space Flight Center and Langley Research Center), Thiokol Corporation, the University of Alabama in Huntsville, AC Engineering, SAIC, Martin Marietta, and Aerojet. The team's purpose was to bring together the appropriate personnel to determine what surface inspection techniques were applicable to multiprogram bonding surface cleanliness inspection. In order to identify appropriate techniques and their sensitivity to various contaminant families, calibration standards were developed. Producing standards included development of consistent low level contamination application techniques. Oxidation was also considered for effect on inspection equipment response. Ellipsometry was used for oxidation characterization. Verification testing was then accomplished to show that selected inspection techniques could detect subject contaminants at levels found to be detrimental to critical bond systems of interest. Once feasibility of identified techniques was shown, selected techniques and instrumentation could then be incorporated into a multipurpose inspection head and integrated with a robot for critical surface inspection. Inspection techniques currently being evaluated include optically stimulated electron emission (OSEE); near infrared (NIR) spectroscopy utilizing fiber optics; Fourier transform infrared (FTIR) spectroscopy; and ultraviolet (UV) fluorescence. Current plans are to demonstrate an integrated system in MSFC's Productivity Enhancement Complex within five years from initiation of this effort in 1992 assuming appropriate funding levels are maintained. This paper gives an overview of work accomplished by the team and future plans.

Burns, H. Dewitt↗

Surface inspection using FTIR spectroscopy

The use of reflectance Fourier transform infrared (FTIR) spectroscopy as a tool for surface inspection is described. Laboratory instruments and portable instruments can support remote sensing probes that can map chemical contaminants on surfaces with detection limits under the best of conditions in the sub-nanometer range, i.e.. near absolute cleanliness, excellent performance in the sub-micrometer range, and useful performance for films tens of microns thick. Examples of discovering and quantifying contamination such as mineral oils and greases, vegetable oils, and silicone oils on aluminum foil, galvanized sheet steel, smooth aluminum tubing, and sandblasted 7075 aluminum alloy and D6AC steel. The ability to map in time and space the distribution of oil stains on metals is demonstrated. Techniques associated with quantitatively applying oils to metals, subsequently verifying the application, and non-linear relationships between reflectance and the quantity oil are described.

Powell, G. L.↗

Attachment of Single-wall Carbon Nanotubes (SWNTs) on Platinum Surfaces by Self-Assembling Techniques

Single-wall carbon nanotubes (SWNTs) are very interesting materials because of their morphology, electronic and mechanical properties. Its morphology (high length-to-diameter ratio) and electronic properties suggest potential application of SWNTs as anode material for lithium ion secondary batteries. The introduction of SWNTs on these types of sources systems will improve their performance, efficiency, and capacity to store energy. A purification method has been applied for the removal of iron and amorphous carbon from the nanotubes. Unpurified and purified SWNTs were characterized by transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). In order to attach carbon nanotubes on platinum electrode surfaces, a self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) was deposited over the electrodes. The amino-terminated SAM obtained was characterized by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and Fourier-transforms infrared (FTIR) spectroscopy. Carbon nanotubes were deposited over the amino-terminated SAM by an amide bond formed between SAM amino groups and carboxylic acid groups at the open ends of the carbon nanotubes.This deposition was characterized using Raman spectroscopy and Scanning Electron microscopy (SEM).

Rosario-Castro, Belinda I.↗

Extreme Thermal Stabilization of Carborane–Cyanate Composites via B–N Dative-Bonded Boroxine Barriers

Enhancing the thermal stability of cyanate ester (CE) resins is crucial for high-temperature aerospace applications. This study elucidates the degradation mechanisms of CE composites reinforced with carborane additives, focusing on the formation of boron–nitrogen (B–N) dative bonds and their role in improving thermal resistance. Using thermogravimetric analysis, we examined char formation and evolved gases at multiple degradation stages. Reaction sequences and char products were characterized via Fourier transform infrared spectroscopy (FTIR), solid-state 13C and 11B NMR, and evolved gas analysis using mass spectrometry and FTIR. The solid-state 11B NMR was instrumental in detecting various boron oxidation states and the formation of B–N dative bonds during decomposition. These bonds facilitate cross-linking in the char phase, enhancing material integrity at elevated temperatures. However, in inert environments, the volatility of boron additives like carborane limits their effectiveness. These findings advance the understanding of CE composite degradation mechanisms and offer critical insights for developing high-temperature-resistant materials for aerospace applications.

Fourier transform infrared spectroscopy↗

Probing Alkylpolyglycoside Hydrogen Bonding and Its Destabilization by Sulfonate Hydrotropes with X‑ray and Vibrational Spectroscopy

It has been proposed that intersurfactant H-bonding networks can produce highly stable foams, specifically those generated from solutions containing alkylpolyglycoside surfactants. In this work, we aim to characterize the presence and destabilization of these networks by introducing a hydrotrope (sodium p-toluene sulfate) at various concentrations into an alkylpolyglycoside (Glucopon 225 DK) surfactant containing solution. Solution surface properties are probed by using aerosol velocity map imaging X-ray photoelectron spectroscopy (A-VMI-XPS) and tensiometer measurements. Bulk properties below the surface are probed using Fourier transform infrared spectroscopy (FTIR) and C-edge near-edge X-ray fine structure spectroscopy (NEXAFS). The surface measurements provide the framework to describe the destabilization of the solution H-bonding network, while the bulk solution measurements provide hints about the disruption of the hydrogen bonding network upon hydrotrope addition. The collected data support the hypothesis that the destabilization of the intersurfactant H-bonding network frees surfactant molecules from the bulk, increasing surfactant population at the air/water interface. This was quantified through an increase in peak area and width in XPS measurements as well as a decrease in surfactant critical micelle concentration. Three regimes with increasing amounts of hydrotrope addition are suggested, described as (1) a hydrotrope affecting only surfactant surface properties, (2) a hydrotrope affecting surfactant surface and bulk properties, and (3) hydrotrope-dominated surface and bulk properties. Future studies will characterize foam stability across the hydrotrope concentration regimes to better define correlations between intersurfactant H-bonding networks and foam stability.

Molecules↗

Characterizing Nanophase Materials on Mars: Spectroscopic Studies of Allophane and Imogolite

Allophane is an amorphous or poorly crystalline hydrous aluminosilicate material. Allophane's chemical structure represents a hollow nanosphere, 5-6 nm in diameter with 4-7 large pores in the structure. Identification of allophane and other amorphous and nanophase minerals on Mars has provided clues about the aqueous geochemical environment there. These materials likely represent partially altered or leached basaltic ash and therefore, could represent a geologic marker for where water was present on the Martian surface; as well as indicate regions of climate change, where surface water was not present long enough or sufficiently warm to form clays. Characterization of these materials is important for increasing spectral recognition capabilities using visible/near-infrared (VNIR) and thermal infrared (TIR) spectra of Mars. A suite of synthetic allophane samples was created using a method that has been modified to produce allophane with Fe isomorphically substituted for Al in octahedral coordination. Compositions of the materials range from high-Si allophane (molar Al:Si = 1:2) to protoimogolite (Al:Si = 2:1), with Fe(3+) and Fe(2+) isomorphically substituted for Al from 0-10 mol% of total Al. These compositions span the range observed in natural terrestrial allophanes. Fe K-edge X-ray absorption spectroscopy provided information on the speciation and electrochemical and structural position of Fe in the framework. Fourier transform infrared spectroscopy confirmed syntheses and demonstrated changes in infrared spectroscopic signature with Fe substitution. VNIR reflectance spectra and TIR Thermal infrared emissivity spectra were also collected for direct comparison to Martian data. By increasing spectral recognition capacities of nanophase materials, more accurate estimates can be made on the aqueous geochemical environment of Mars.

Jeute, Thomas↗

Molecular structures of residual solvent in polyacrylonitrile based electrolytes: Implications for conductivity and stability

Lithium-ion batteries increasingly play significant roles in modern technologies; however, increased energy density also raises concerns about electrolyte safety. Traditional electrolytes that use volatile organic solvents face risks of thermal runaways and fires from electrode shorting. In response, polymer-based solid electrolytes have been developed for replacement. Polyacrylonitrile (PAN) is a promising fire-resistant component for electrolyte fabrication, but its limited solubility necessitates using low-volatility solvents, which are notoriously difficult to remove in subsequent drying processes. Here, we use femtosecond two-dimensional infrared spectroscopy to provide an in-depth understanding of how residual solvent from processing affects the molecular structures and dynamics within a polymer electrolyte. To this end, linear and nonlinear infrared spectroscopies are employed to interrogate the molecular interactions in PAN-based electrolytes containing various contents of N,N-dimethylformamide (DMF). We show that the amount of DMF within the PAN electrolyte affects the Li+ structure. Further, the coordination can proceed through the carbonyl group and/or the amide nitrogen to form antiparallel structures with the nitrile groups of PAN through dipole–dipole interactions. The free motion of DMF is drastically inhibited upon interaction with Li+ and PAN, which decreases the ionic conductivity and potentially affects the stability (resistance toward removal and chemical decomposition). These findings have implications for the design and processing of solid polymer electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗

Performance and Analysis of Perfluoropolyalkyl Ether Grease Used on Space Shuttle Actuators--A Case Study

Actuators used on the United States space shuttle fleet are lubricated with unspecified amounts of Braycote 601 (Castrol Braycote) grease consisting of a perfluoropolyalkyl ether (PFPAE) base oil thickened with a polytetrafluoroethylene (PTFE) filler. Each shuttle has four body flap actuators (BFAs) (two on each wing) on a common segmented shaft and four rudder speed brake (RSB) actuators. The actuators were designed to operate for 10 years and 100 flights without periodic relubrication. Visible inspection of two partially disassembled RSB actuators in continuous use for 19 years raised concerns over possible grease degradation due to discoloration of the grease on several places on the surfaces of the gears. Inspection revealed fretting, micropitting, wear and corrosion of the bearings and gears. A small amount of oil dripped from the disassembled actuators. Whereas new grease is beige in appearance, the discolored grease consisted of both grey and reddish colors. Grease samples taken from the actuators together with representative off-the-shelf new and unused grease samples were analyzed by gravimetry for oil content; by inductively coupled plasma spectroscopy (ICP) for metals content; Fourier transform infrared (FTIR) spectroscopy for base oil decomposition; and by size exclusion chromatography (SEC) for determination of the molecular weight distributions of the grease oil. The Braycote 601 grease was stable after 19 years of continuous use in the sealed RSB actuators and was fit for its intended purpose. There were no significant chemical differences between the used grease samples and new and unused samples. Base oil separation was not significant within the sealed actuators. No corrosive effect in the form of iron fluoride was detected. The grey color of grease samples was due to metallic iron. The red color was due to oxidation of the metallic wear particles from the gears and the bearings comprising the actuators.

Morales, Wilfredo↗

Broadband Rotational Spectroscopy in Uniform Supersonic Flows: Chirped Pulse/Uniform Flow for Reaction Dynamics and Low Temperature Kinetics

ConspectusThe study of gas-phase chemical reactions at very low temperatures first became possible with the development and implementation of the CRESU (French acronym for Reaction Kinetics in Uniform Supersonic Flows) technique. CRESU relies on a uniform supersonic flow produced by expansion of a gas through a Laval (convergent-divergent) nozzle to produce a wall-less reactor at temperatures from 10 to 200 K and densities of 1016-1018 cm-3 for the study of low temperature kinetics, with particular application to astrochemistry. In recent years, we have combined uniform flows with revolutionary advances in broadband rotational spectroscopy to yield an instrument that affords near-universal detection for novel applications in photodissociation, reaction dynamics, and kinetics. This combination of uniform supersonic flows with chirped-pulse Fourier-transform microwave spectroscopy (Chirped-Pulse/Uniform Flow, CPUF) permits detection of any species with a modest dipole moment, thermalized to the uniform temperature of the gas flow, with isomer, conformer, and vibrational state specificity. In addition, the use of broadband, high-resolution, and time-dependent (microsecond time scale) micro- and mm-wave spectroscopy makes it an ideal tool for characterizing both transient and stable molecules, as well as studying their spectroscopy and dynamics.In this Account, we review recent advances made using the CPUF technique, including studies of photodissociation, radical-radical reaction dynamics, and low temperature kinetics. These studies highlight both the strength of universal and multiplexed detection and the challenges of coupling it to a high-density collisional environment. Product branching and product evolution as a function of time have been measured for astrochemically relevant systems, relying on the detailed characterization of these flow conditions via experiments and fluid dynamics simulations. In the photodissociation of isoxazole, an unusual heterocyclic molecule with a very low-energy conical intersection, we have identified 7 products in 5 reaction channels and determined the product branching, pointing to both direct and indirect pathways. We have also approached the same system from separated NO and C3H3 reactants to explore a broader range of the potential energy surface, demonstrating the power of multichannel branching measurements for complex radical-radical reactions. We determined the product branching in the C3H2 isomers in the photodissociation of the propargyl radical and identified the importance of a hydrogen atom catalyzed isomerization to the lowest energy cyclic form. This then motivated a study of direct D-H exchange reaction in radicals, in which we demonstrate that it is an important and overlooked pathway for deuterium fractionation in astrochemical environments. Recently, we have shown the measurement of low temperature kinetics inside an extended Laval nozzle, after which a shock-free secondary expansion to low temperature and density affords an ideal environment for detection by rotational spectroscopy. These results highlight the power and potential of the CPUF approach, and future prospects will also be discussed in light of these developments.

Dias, Nureshan↗

An infrared, Raman, and X-ray database of battery interphase components

Further improvements to lithium-ion and emerging battery technologies can be enabled by an improved understanding of the chemistry and working mechanisms of interphases that form at electrochemically active battery interfaces. However, it is difficult to collect and interpret spectra of interphases for several reasons, including the presence of a variety of compounds. To address this challenge, we herein present a vibrational spectroscopy and X-ray diffraction data library of ten compounds that have been identified as interphase constituents in lithium-ion or emerging battery chemistries. The data library includes attenuated total reflectance Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray diffraction data, collected in inert atmospheres provided by custom sample chambers. The data library presented in this work (and online repository) simplifies access to reference data that is otherwise either diffusely spread throughout the literature or non-existent, and provides energy storage researchers streamlined access to vital interphase-relevant data that can accelerate battery research efforts.

25 ENERGY STORAGE↗

Raman spectroscopy of gases with a Fourier transform spectrometer - The spectrum of D2

Fourier transform spectrometry (FTS) is presently used to record the spontaneous incoherent laser Raman spectra of gases. The high resolution, sensitivity, calibration accuracy and spectral coverage achieved demonstrate the viability of FTS for Raman spectroscopy. Attention is given to the coefficients obtained by fitting measurements obtained from the spectrum of D2, containing both v = 0-0 and 1-0 transitions, to the Dunham (1932) expansion of the vibration-rotation energy levels.

Jennings, D. E.↗

Optical spectroscopy of interplanetary dust collected in the earth's stratosphere

Optical absorption spectra of interplanetary dust particles 2-30 microns in size collected in the atmosphere at an altitude of 20 km by inertial impactors mounted on NASA U-2 aircraft are reported. Fourier transform absorption spectroscopy of crushed samples of the particles reveals a broad feature in the region 1300-800 kaysers which has also been found in meteorite and cometary dust spectra, and a weak iron crystal field absorption band at approximately 9800 kaysers, as is observed in meteorites. Work is currently in progress to separate the various components of the interplanetary dust particles in order to evaluate separately their contributions to the absorption.

Fraundorf, P.↗

Absolute band intensities in the nu19/nu23 (530 cm(-1)) and nu7 (777 cm(-1)) bands of acetone ((CH3)2CO) from 232 to 295 K

Absolute band intensities of acetone ((CH3)2CO) in the nu19/nu23 and nu7 band systems near 530 and 777 cm(-1), respectively, were measured at temperatures of 232, 262 and 295 K, using a Fourier transform infrared (FTIR) spectrometer. No evident temperature dependence for the band intensities was observed. The dipole moments and the fundamental band intensities were derived in the harmonic oscillator approximation. The results are useful for the spectroscopic retrieval of acetone concentrations in the upper atmosphere.

Acetone/chemistry↗

Geophysical Impacts and Spectroscopic Identification of a Hydrous Iron Sulfate on Icy Worlds

Over geologic time-scales, large volumes of exogenic sulfur ions from Io's plasma torus have been supplied to the surface of Europa and Ganymede, which, combined with recent interpretations of orbiter images, dynamical modeling, and surface-subsurface exchange, suggests further sulfur transport into the interior of the icy worlds. These observations motivate mixed-phase spectral modeling for interpreting orbiter spectroscopy data and determination of hydration states of candidate surface materials including hydrous sulfates. In this work, we present a combined experimental and theoretical study of the low temperature and high pressure vibrational spectral signature of the iron-sulfate monohydrate endmember, szomolnokite (FeSO 4 ·H 2 O). By employing synchrotron Fourier-transform infrared spectroscopy (FTIR) in the diamond anvil cell up to 23 GPa and down to 20 K, we explore the extreme range of pressure-temperature domains relevant to icy environments throughout our solar system and beyond. Combined with our density-functional theory quantum-mechanics molecular dynamics results, we demonstrate that experimentally observed infrared features in the O-H stretching region commonly associated with nH 2 O (n > 1) hydration states can be attributed to a pure monohydrate without the need for pressure-induced exsolved ice, other coexisting hydrous iron sulfates, or strong overtone and combination modes. We further discuss the possibility of lateral variations in density and shear properties on icy worlds associated with temperature variations and the high-pressure phases of kieserite group monohydrated sulfates.

Geosciences↗

Ultrabroadband THz conductivity of gated graphene in- and out-of-equilibrium

We employ ultrabroadband terahertz (THz) spectroscopy to expose the high-frequency transport properties of Dirac fermions in monolayer graphene. By controlling the carrier concentration via tunable electrical gating, both equilibrium and transient optical conductivities are obtained for a range of Fermi levels. The frequency-dependent equilibrium response is determined through a combination of time-domain THz and Fourier-transform infrared spectroscopy for energies up to the near-infrared, which also provides a measure of the gate-voltage dependent Fermi level. Transient changes in the real and imaginary parts of the graphene conductivity are electro-optically resolved for frequencies up to 15 THz after near-infrared femtosecond excitation, both at the charge-neutral point and for higher electrostatic-doping levels. Modeling of the THz response provides insight into changes of the carrier spectral weights and scattering rates, and reveals an additional broad-frequency ($$\approx$$ 8 THz) component to the photo-induced response, which we attribute to the zero-momentum mode of quantum-critical transport observed here in large-area CVD graphene.

Coslovich, G↗

Fourier-transform optical microsystems

The design, fabrication, and initial characterization of a miniature single-pass Fourier-transform spectrometer (FTS) that has an optical bench that measures 1 cm x 5 cm x 10 cm is presented. The FTS is predicated on the classic Michelson interferometer design with a moving mirror. Precision translation of the mirror is accomplished by microfabrication of dovetailed bearing surfaces along single-crystal planes in silicon. Although it is miniaturized, the FTS maintains a relatively high spectral resolution, 0.1 cm-1, with adequate optical throughput.

NASA Discipline Environmental Health↗

Pressure Sounding of the Middle Atmosphere from ATMOS Solar Occultation Measurements of Atmospheric CO(sub 2) Absorption Lines

A method for retrieving the atmospheric pressure corresponding to the tangent point of an infrared spectrum recorded in the solar occultation mode is described and applied to measurements made by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer. Tangent pressure values are inferred from measurements of isolated CO(sub 2) lines with temperature-insensitive intensities. Tangent pressures are determined with a spectroscopic precision of 1-3%, corresponding to a tangent point height precision, depending on the scale height, of 70-210 meters.

Atmospheric Trace Molecule Spectroscopy ATMOS atmo↗