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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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DOE OSTI2026

Efficient Low-Temperature Direct Lithium Extraction from Chloride Brines Enabled by High-Capacity Sorbent

The demand for lithium, a key component in rechargeable batteries for electric vehicles and renewable energy storage systems, has surged in recent years. Meeting this demand requires efficient extraction methods that are both environmentally friendly and economically viable. This study investigates the utilization of the high-capacity sorbent amorphous aluminum hydroxide for enabling efficient direct lithium extraction at low temperatures. Traditional extraction methods often involve acid-leaching and energy-intensive processes that are not only expensive but also environmentally taxing. In contrast, our approach leverages the exceptional sorption properties of amorphous aluminum hydroxide to facilitate lithium extraction directly from brine, achieving extraction efficiencies of 94.4% in case 1 and 96.2% in case 2 at low temperatures. Kinetic modeling using the Avrami–Erofe’ev framework reveals a nucleation-growth mechanism ( n = 0.71, k = 0.131 h –1 ), providing quantitative insights into the solid-state phase transformation process. This method significantly reduces energy consumption and minimizes the environmental footprint. Through systematic experimentation and optimization, we demonstrate the effectiveness and scalability of our approach, highlighting its potential to revolutionize lithium extraction processes. Our findings highlight the potential of high-capacity sorbents, particularly amorphous aluminum hydroxide toward sustainable lithium production, contributing to the advancement of clean-energy technologies.

anions↗
DOE OSTI2020

Synthesis, Characterization, and Utilization of a Lignin-Based Adsorbent for Effective Removal of Azo Dye from Aqueous Solution

How to effectively remove toxic dyes from the industrial wastewater using a green low-cost lignocellulose-based adsorbent, such as lignin, has become a topic of great interest but remains quite challenging. In this study, cosolvent-enhanced lignocellulosic fractionation (CELF) pretreatment and Mannich reaction were combined to generate an aminated CELF lignin which is subsequently applied for removal of methylene blue and direct blue (DB) 1 dye from aqueous solution. 31P NMR was used to track the degree of amination, and an orthogonal design was applied to determine the relationship between the extent of amination and reaction parameters. The physicochemical, morphological, and thermal properties of the aminated CELF lignin were characterized to confirm the successful grafting of diethylenetriamine onto the lignin. The aminated CELF lignin proved to be an effective azo dye-adsorbent, demonstrating considerably enhanced dye decolorization, especially toward DB 1 dye (>90%). It had a maximum adsorption capacity of DB 1 dye of 502.7 mg/g, and the kinetic study suggested the adsorption process conformed to a pseudo-second-order kinetic model. The isotherm results also showed that the modified lignin-based adsorbent exhibited monolayer adsorption. The adsorbent properties were mainly attributed to the incorporated amine functionalities as well as the increased specific surface area of the aminated CELF lignin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Chemical Kinetics of the Autoxidation of Poly(ethylenimine) in CO 2 Sorbents

The oxidative degradation rates of a CO 2 sorbent composed of a mesoporous alumina impregnated with poly- (ethylenimine) (PEI) are measured under systematically varied conditions and a reaction rate law is created. Good agreement is shown between the rate of oxidation obtained via in situ calorimetric heat measurement during oxidative degradation reactions and the loss of CO 2 capture performance presented as amine efficiency (mol CO 2 /mol amine). PEI mass loss and elemental composition are tracked over the course of the reaction and used in conjunction with the oxidation rate measurements to shed insight into the oxidation reaction(s). These data, in combination with measurements of the heat of reaction, suggest a common reaction set across the range of temperatures, oxygen concentrations, and sorbent compositions tested. The data are consistent with the basic autoxidation scheme (BAS), the accepted mechanism of autoxidation of aliphatic polymers. We propose a lumped kinetic model to describe the oxidation reaction set and estimate an activation energy of 105 kJ/mol and an oxygen reaction order of 0.5–0.7 from the data accordingly. Furthermore, these parameters can be incorporated into process cycle models to estimate the material lifetime, a critical uncertainty in the deployment of DAC technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Systems-Level Modeling for CRISPR-Based Metabolic Engineering

The CRISPR-Cas system has enabled the development of sophisticated, multigene metabolic engineering programs through the use of guide RNA-directed activation or repression of target genes. To optimize biosynthetic pathways in microbial systems, we need improved models to inform design and implementation of transcriptional programs. Recent progress has resulted in new modeling approaches for identifying gene targets and predicting the efficacy of guide RNA targeting. Genome-scale and flux balance models have successfully been applied to identify targets for improving biosynthetic production yields using combinatorial CRISPR-interference (CRISPRi) programs. Here, the advent of new approaches for tunable and dynamic CRISPR activation (CRISPRa) promises to further advance these engineering capabilities. Once appropriate targets are identified, guide RNA prediction models can lead to increased efficacy in gene targeting. Developing improved models and incorporating approaches from machine learning may be able to overcome current limitations and greatly expand the capabilities of CRISPR-Cas9 tools for metabolic engineering.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Chemical Modifications of Ag Catalyst Surfaces with Imidazolium Ionomers Modulate H 2 Evolution Rates during Electrochemical CO 2 Reduction

Bridging polymer design with catalyst surface science is a promising direction for tuning and optimizing electrochemical reactors that could impact long-term goals in energy and sustainability. Particularly, the interaction between inorganic catalyst surfaces and organic-based ionomers provides an avenue to both steer reaction selectivity and promote activity. In this work, we studied the role of imidazolium-based ionomers for electrocatalytic CO 2 reduction to CO (CO 2 R) on Ag surfaces and found that they produce no effect on CO 2 R activity yet strongly promote the competing hydrogen evolution reaction (HER). By examining the dependence of HER and CO 2 R rates on concentrations of CO 2 and HCO 3 –, we developed a kinetic model that attributes HER promotion to intrinsic promotion of HCO 3 – reduction by imidazolium ionomers. We also show that varying the ionomer structure by changing substituents on the imidazolium ring modulates the HER promotion. This ionomer-structure dependence was analyzed via Taft steric parameters and density functional theory calculations, which suggest that steric bulk from functionalities on the imidazolium ring reduces access of the ionomer to both HCO 3 – and the Ag surface, thus limiting the promotional effect. Our results help develop design rules for ionomer–catalyst interactions in CO 2 R and motivate further work into precisely uncovering the interplay between primary and secondary coordination in determining electrocatalytic behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Spontaneous Reorganization of DNA-Based Polymers in Higher Ordered Structures Fueled by RNA

We demonstrate a strategy that allows for the spontaneous reconfiguration of self-assembled DNA polymers exploiting RNA as chemical fuel. To do this, we have rationally designed orthogonally addressable DNA building blocks that can be transiently deactivated by RNA fuels and subtracted temporarily from participation in the self-assembly process. Through a fine modulation of the rate at which the building blocks are reactivated we can carefully control the final composition of the polymer and convert a disordered polymer in a higher order polymer, which is disfavored from a thermodynamic point of view. We measure the dynamic reconfiguration via fluorescent signals and confocal microscopy, and we derive a kinetic model that captures the experimental results. Our approach suggests a novel route toward the development of biomolecular materials in which engineered chemical reactions support the autonomous spatial reorganization of multiple components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Size-Controlled Nanoparticles Embedded in a Mesoporous Architecture Leading to Efficient and Selective Hydrogenolysis of Polyolefins

A catalytic architecture, comprising a mesoporous silica shell surrounding platinum nanoparticles (NPs) supported on a solid silica sphere (mSiO2/Pt-X/SiO2; X is the mean NP diameter), catalyzes hydrogenolysis of melt-phase polyethylene (PE) into a narrow C23-centered distribution of hydrocarbons in high yield using very low Pt loadings (~10 -5 g Pt/g PE). During catalysis, a polymer chain enters a pore and contacts a Pt NP where the C–C bond cleavage occurs and then the smaller fragment exits the pore. mSiO 2 /Pt/SiO 2 resists sintering or leaching of Pt and provides high yields of liquids; however, many structural and chemical effects on catalysis are not yet resolved. Here, we report the effects of Pt NP size on activity and selectivity in PE hydrogenolysis. Time-dependent conversion and yields and a lumped kinetics model based on the competitive adsorption of long vs short chains reveal that the activity of catalytic material is highest with the smallest NPs, consistent with a structure-sensitive reaction. Remarkably, the three mSiO 2 /Pt-X/SiO 2 catalysts give equivalent selectivity. We propose that mesoscale pores in the catalytic architecture template the C 23 -centered distribution, whereas the active Pt sites influence the carbon–carbon bond cleavage rate. This conclusion provides a framework for catalyst design by separating the C–C bond cleavage activity at catalytic sites from selectivity for chain lengths of the products influenced by the structure of the catalytic architecture. The increased activity, selectivity, efficiency, and lifetime obtained using this architecture highlight the benefits of localized and confined environments for isolated catalytic particles under condensed-phase reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Pt Particle Size Affects Both the Charge Separation and Water Reduction Efficiencies of CdS–Pt Nanorod Photocatalysts for Light Driven H 2 Generation

Decreasing the metal catalyst size into nanoclusters or even single atom is an emerging direction of developing more efficient and cost-effective photocatalytic systems. Because the catalyst particle size affects both the catalyst activity and light driven charge separation efficiency, their effects on the overall photocatalytic efficiency are still poorly understood. Herein, using a well-defined semiconductor–metal heterostructure with Pt nanoparticle catalysts selectively grown on the apexes of CdS nanorods (NRs), we study the effect of the Pt catalyst size on light driven H 2 generation quantum efficiency (QE H 2 ). With the increase of the Pt catalyst size from 0.7 ± 0.3 to 3.0 ± 0.8 nm, the QEH 2 of CdS–Pt increases from 0.5 ± 0.2% to 38.3 ± 5.1%, by nearly 2 orders of magnitude. Transient absorption spectroscopy measurement reveals that the electron transfer rate from the CdS NR to the Pt tip increases with the Pt diameter following a scaling law of d 5.6 , giving rise to the increase of electron transfer efficiency at larger Pt sizes. Additionally, the observed trend can be understood by a simplified kinetic model that assumes the overall efficiency is the product of the quantum efficiencies of charge separation (including hole transfer, electron transfer, and hole scavenging) and water reduction steps, and for CdS–Pt NRs, the quantum efficiencies of electron transfer and water reduction steps increase with the Pt sizes. Our findings suggest the importance of improving the quantum efficiencies of both charge separation and catalysis in designing efficient semiconductor–metal hybrid photocatalysts, especially in the regime of small metal particle sizes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Direct Observation of Solvent–Reaction Intermediate Interactions in Heterogeneously Catalyzed Alcohol Coupling

The relative stability of reactive intermediates and reactants on a surface, which dictates the rate and selectivity of catalytic reactions in both gas and liquid phases, is dependent on numerous factors. One well-established example is secondary interactions, such as van der Waals interactions between the catalyst surface and the pendant group of the intermediate, which can govern reaction selectivity for coupling reactions. In this work, we directly show that interactions between adsorbed reaction intermediates and reactant molecules increase the binding energy and affects the geometrical arrangement of coadsorbed reactant/solvent molecules. Evidence for this effect is demonstrated for the oxidative coupling reaction of methanol on a single crystal gold (Au(110)) surface. The rate-limiting reaction intermediate for methanol selfcoupling, methoxy, stabilizes excess adsorbed methanol, which desorbs as a result of beta-hydride decomposition of the adsorbed methoxy. Direct molecular-scale imaging by scanning tunneling microscopy, supplemented by density functional theory, revealed interactive structures formed by methoxy and coadsorbed methanol. Interactions between the methoxy intermediate and coadsorbed methanol stabilizes a hydrogen-bonded network comprising methoxy and methanol by a minimum of 0.13 eV per methanol molecule. Inclusion of such interactions between reaction intermediates and coadsorbed reactants and solvents in kinetic models is important for microkinetic analysis of the rates and selectivities of catalytic reactions in both the gas and liquid phases whenever appreciable coverages of species from the ambient phase exist.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Highly Active and Selective Sites for Propane Dehydrogenation in Zeolite Ga-BEA

A highly selective Ga-modified zeolite BEA for propane dehydrogenation has been synthesized by grafting Ga on Zn-BEA followed by removal of Zn in the presence of H 2 . A propene selectivity of 82% at 19% propane conversion illustrates the high selectivity at 813 K. The kinetic model of the catalyzed dehydrogenation including the elementary steps of propane adsorption, first and second C–H bond cleavage, and propene and H 2 desorption demonstrates that the propane dehydrogenation rate is determined by the first C–H bond cleavage at low pC 3 H 8 , while at high pC 3 H 8 , the rate is limited by the desorption of H 2 . The active sites have been identified as dehydrated and tetrahedrally coordinated Ga 3+ in the *BEA lattice. Furthermore, the low selectivity toward aromatics is concluded to be associated with the high Lewis acid strength of lattice Ga 3+ and the low Brønsted acid strength of the hydrated Ga sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering: Influence of Precursors and Cations on the Reaction Pathway

Iridium nanoparticles are important catalysts for several chemical and energy conversion reactions. Studies of iridium nanoparticles have also been a key for the development of kinetic models of nanomaterial formation. However, compared to other metals such as gold or platinum, knowledge on the nature of prenucleation species and structural insights into the resultant nanoparticles are missing, especially for nanoparticles obtained from Ir$_x$Cl$_y$ precursors investigated here. We use in situ X-ray total scattering (TS) experiments with pair distribution function (PDF) analysis to study a simple, surfactant-free synthesis of colloidal iridium nanoparticles. The reaction is performed in methanol at 50 °C with only a base and an iridium salt as precursor. From different precursor salts–IrCl 3 , IrCl 4 , H 2 IrCl 6 , or Na 2 IrCl 6 –colloidal nanoparticles as small as Ir ~55 are obtained as the final product. The nanoparticles do not show the bulk iridium face-centered cubic ($fcc$) structure but show decahedral and icosahedral structures. The formation route is highly dependent on the precursor salt used. Using IrCl 3 or IrCl 4 , metallic iridium nanoparticles form rapidly from Ir$_x$Cl$_y$$^{n–}$ complexes, whereas using H 2 IrCl 6 or Na 2 IrCl 6 , the iridium nanoparticle formation follows a sudden growth after an induction period and the brief appearance of a crystalline phase. With H 2 IrCl 6 , the formation of different Ir$_n$ ($n$ = 55, 55, 85, and 116) nanoparticles depends on the nature of the cation in the base (LiOH, NaOH, KOH, or CsOH, respectively) and larger particles are obtained with larger cations. As the particles grow, the nanoparticle structure changes from partly icosahedral to decahedral. In conclusion, the results show that the synthesis of iridium nanoparticles from Ir$_x$Cl$_y$ is a valuable iridium nanoparticle model system, which can provide new compositional and structural insights into iridium nanoparticle formation and growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Bulky Phosphine Ligands Promote Palladium-Catalyzed Protodeboronation

The Suzuki-Miyaura cross-coupling reaction is plagued by protodeboronation, an undesirable side reaction with water that consumes the boronic acid derivatives required for the cross-coupling reaction. Meticulous mechanistic studies have previously established protodeboronation to be highly sensitive to the nature of the boronic reagent and reaction conditions. Particularly, the presence of bases, which are essential for the Suzuki-Miyaura coupling, is known to catalyze protodeboronation. However, protodeboronation catalyzed by palladium-phosphine complexes, the benchmark catalyst system for Suzuki-Miyaura cross-coupling, has been understudied compared to its base-catalyzed counterpart. Here, we demonstrate, using automated high-throughput experimentation, comprehensive computational mechanistic analyses and kinetic modeling, that protodeboronation is accelerated by palladium(II) complexes bound to bulky phosphine ligands. While sterically hindered ligands are typically used to facilitate difficult cross-couplings, these ligands can instead paradoxically impede cross-coupling product formation, requiring careful and judicious consideration when choosing ligands for Suzuki-Miyaura cross-couplings.

Ser, Cher Tian [University of Toronto, ON (Canada)↗
DOE OSTI2017

Mechanism of Nitrogenase H 2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

Nitrogenase catalyzes the reduction of dinitrogen (N2) to ammonia (NH3) with obligatory reduction of protons (H+) to dihydrogen (H2) through a mechanism involving reductive elimination of two [Fe-H-Fe] bridging hydrides at its active site FeMo-cofactor. The overall rate-limiting step is associated with ATP-driven electron delivery from Fe protein, precluding isotope effect measurements on substrate reduction steps. Here, we use mediated bioelectrocatalysis to drive electron delivery to MoFe protein without Fe protein and ATP hydrolysis, thereby eliminating the normal rate-limiting step. The ratio of catalytic current in mixtures of H2O and D2O, the proton inventory, changes linearly with the D2O/H2O ratio, revealing that a single H/D is involved in the rate limiting step. Kinetic models, along with measurements that vary the electron/proton delivery rate and use different substrates, reveal that the rate-limiting step under these conditions is the H2 formation reaction. Altering the chemical environment around the active site FeMo-cofactor in the MoFe protein either by substituting nearby amino acids or transferring the isolated FeMo-cofactor into a different peptide matrix, changes the net isotope effect, but the proton inventory plot remains linear, consistent with an unchanging rate-limiting step. Density functional theory predicts a transition state for H2 formation where the proton from S-H+ moves to the hydride in Fe-H-, predicting the number and magnitude of the observed H/D isotope effect. This study not only reveals the mechanism of H2 formation, but also illustrates a strategy for mechanistic study that can be applied to other enzymes and to biomimetic complexes.

BINDING↗
DOE OSTI2018

Ultrafast Photophysics of a Dinitrogen-Bridged Molybdenum Complex

Among the many metal–dinitrogen complexes synthesized, the end-on bridging (μ 2 , η 1 , η 1 —N 2 ) coordination mode is notoriously unreactive for nitrogen fixation. This is principally due to the large activation energy for ground-state nitrogen–element bond formation and motivates exploration of the photoexcited reactivity of this coordination mode. To provide the foundation for this concept, the photophysics of a dinitrogen-bridged molybdenum complex was explored by ultrafast electronic spectroscopies. The complex absorbs light from the UV to near-IR, and the transitions are predominantly of metal-to-ligand charge transfer (MLCT) character. Five excitation wavelengths (440, 520, 610, 730, and 1150 nm) were employed to access MLCT bands, and the dynamics were probed between 430 and 1600 nm. Despite the large energy space occupied by electronic states (ca. 1.2 eV), the dynamics were independent of the excitation wavelength. In the proposed kinetic model, photoexcitation from a Mo–N=N–Mo centered ground state populates the π*-state delocalized over two terpyridine ligands. Due to a large terpyridine–terpyridine spatial separation, electronic localization occurs within 100 fs, augmented by symmetry breaking. The subsequent interplay of internal conversion and intersystem crossing (ISC) populates the lowest 3 MLCT state in 2–3 ps. Decay to the ground state occurs either directly or via a thermally activated metal-centered ( 3 MC) trap state having two time constants (10–15 ps, 23–26 ps [298 K]; 103 ps, 612 ps [77 K]). ISC between 1 MLCT and 3 MLCT involves migration of energized electron density from the terpyridine π* orbitals to the Mo–N=N–Mo core. As a result, implication of the observed dynamics for the potential N–H bond forming reactivity are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A Geo‐Structurally Based Correction Factor for Apparent Dissolution Rates in Fractured Media

Abstract Field measurements of apparent geochemical weathering reaction rates in subsurface fractured porous media are known to deviate from laboratory measurements by multiple orders of magnitude. To date, there is no geologically based explanation for this discrepancy that can be used to predict reaction rates in field systems. Proposed correction factors are typically based on ad hoc characterizations related to geochemical kinetic models. Through a series of high‐fidelity reactive transport simulations of mineral dissolution within explicit 3D discrete fracture networks, we are able to link the geo‐structural attributes with reactive transport observations. We develop a correction factor to linear transition state theory for the prediction of the apparent dissolution rate based on measurable geological properties. The modified rate law shows excellent agreement with numerical simulations, indicating that geological structure could be a primary reason for the discrepancy between laboratory and field observations of apparent dissolution rates in fractured media.

58 GEOSCIENCES↗
DOE OSTI2017

Understanding trends in electrochemical carbon dioxide reduction rates

Electrochemical carbon dioxide reduction to fuels presents one of the great challenges in chemistry. Herein we present an understanding of trends in electrocatalytic activity for carbon dioxide reduction over different metal catalysts that rationalize a number of experimental observations including the selectivity with respect to the competing hydrogen evolution reaction. We also identify two design criteria for more active catalysts. The understanding is based on density functional theory calculations of activation energies for electrochemical carbon monoxide reduction as a basis for an electrochemical kinetic model of the process. Furthermore, we develop scaling relations relating transition state energies to the carbon monoxide adsorption energy and determine the optimal value of this descriptor to be very close to that of copper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Low irradiance multiphoton imaging with alloyed lanthanide nanocrystals

Abstract Multiphoton imaging techniques that convert low-energy excitation to higher energy emission are widely used to improve signal over background, reduce scatter, and limit photodamage. Lanthanide-doped upconverting nanoparticles (UCNPs) are among the most efficient multiphoton probes, but even UCNPs with optimized lanthanide dopant levels require laser intensities that may be problematic. Here, we develop protein-sized, alloyed UCNPs (aUCNPs) that can be imaged individually at laser intensities >300-fold lower than needed for comparably sized doped UCNPs. Using single UCNP characterization and kinetic modeling, we find that addition of inert shells changes optimal lanthanide content from Yb 3+ , Er 3+ -doped NaYF 4 nanocrystals to fully alloyed compositions. At high levels, emitter Er 3+ ions can adopt a second role to enhance aUCNP absorption cross-section by desaturating sensitizer Yb 3+ or by absorbing photons directly. Core/shell aUCNPs 12 nm in total diameter can be imaged through deep tissue in live mice using a laser intensity of 0.1 W cm −2 .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Light quantum control of persisting Higgs modes in iron-based superconductors

The Higgs mechanism, i.e., spontaneous symmetry breaking of the quantum vacuum, is a cross-disciplinary principle, universal for understanding dark energy, antimatter and quantum materials, from superconductivity to magnetism. Unlike one-band superconductors (SCs), a conceptually distinct Higgs amplitude mode can arise in multi-band, unconventional superconductors via strong interband Coulomb interaction, but is yet to be accessed. Here we discover such hybrid Higgs mode and demonstrate its quantum control by light in iron-based high-temperature SCs. Using terahertz (THz) two-pulse coherent spectroscopy, we observe a tunable amplitude mode coherent oscillation of the complex order parameter from coupled lower and upper bands. The nonlinear dependence of the hybrid Higgs mode on the THz driving fields is distinct from any known SC results: we observe a large reversible modulation of resonance strength, yet with a persisting mode frequency. Together with quantum kinetic modeling of a hybrid Higgs mechanism, distinct from charge-density fluctuations and without invoking phonons or disorder, our result provides compelling evidence for a light-controlled coupling between the electron and hole amplitude modes assisted by strong interband quantum entanglement. Such light-control of Higgs hybridization can be extended to probe many-body entanglement and hidden symmetries in other complex systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗