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At least 343 records · Page 19

Biocatalytic Yarn for Peroxide Decomposition with Controlled Liquid Transport

In this study, a robust biocatalytic yarn with controllable liquid transport properties is created by coating thin layers of chitosan containing catalase onto a cellulosic yarn. The resulting material integrates enzyme catalytic functionality with protective coating properties of chitosan and structural functionality of the textile. Mild immobilization conditions and good affinity between the two polysaccharides minimize enzyme inactivation during the preparation steps and prevent enzyme from leaching during peroxide decomposition testing and washing, providing a novel and versatile enzyme immobilization strategy. The catalytic efficiency of enzymes in a reaction containing solid, liquid, and gas phases is facilitated when dissolved enzyme substrate is transported by liquid flowing through the coated textile structure. The flow-through configuration decomposes at least two times more peroxide in a twenty-times smaller reaction zone volume compared to a stirred tank configuration. Liquid transport through the yarn and liquid spatial distribution within the yarn are investigated by in situ neutron radiography and neutron computed tomography, revealing a constrained wicking mechanism that benefits biocatalytic yarn performance. This new class of sustainable and flexible biocatalytic textile matrices has beneficial multifunctional properties, not previously described, that are applicable for numerous small- and large-scale applications including controlled flow reactors and reactive filtration.

36 MATERIALS SCIENCE↗

Stabilized Co-Free Li-Rich Oxide Cathode Particles with An Artificial Surface Prereconstruction

Li-rich metal oxide (LXMO) cathodes have attracted intense interest for rechargeable batteries because of their high capacity above 250 mAh g –1 . However, the side effects of hybrid anion and cation redox (HACR) reactions, such as oxygen release and phase collapse that result from global oxygen migration (GOM), have prohibited the commercialization of LXMO. GOM not only destabilizes the oxygen sublattice in cycling, aggravating the well-known voltage fading, but also intensifies electrolyte decomposition and Mn dissolution, causing severe full-cell performance degradation. In this study, an artificial surface prereconstruction (ASR) for Li 1.2 Mn 0.6 Ni 0.2 O 2 particles with a molten-molybdate leaching is conducted, which creates a crystal-dense anion-redox-free LiMn 1.5 Ni 0.5 O 4 shell that completely encloses the LXMO lattice (ASR-LXMO). Differential electrochemical mass spectroscopy and soft X-ray absorption spectroscopy analyses demonstrate that GOM is shut down in cycling, which not only stabilizes HACR in ASR-LXMO, but also mitigates the electrolyte decomposition and Mn dissolution. ASR-LXMO displays greatly stabilized cycling performance as it retains 237.4 mAh g –1 with an average discharge voltage of 3.30 V after 200 cycles. More crucially, while the pristine LXMO cycling cannot survive 90 cycles in a pouch full-cell matched with a commercial graphite anode and lean (2 g A –1 h –1 ) electrolyte, ASR-LXMO shows high capacity retention of 76% after 125 cycles in full-cell cycling.

25 ENERGY STORAGE↗

Molecular Interlocking Multidimensional Modulations of Cathode‐Electrolyte Interface for Constructing High Energy Density Quasi‐Solid‐State Batteries

Gel polymers are regarded as a promising candidate electrolyte for lithium-metal quasi-solid-state batteries, primarily due to their high ionic conductivity and solid-liquid synergistic properties. However, challenges such as interfacial side reactions, limitations in Li + transport caused by interfacial issues, and leaching of transition metals from the cathode have yet to be effectively solved. Herein, a novel gel electrolyte modulation strategy based on electrostatic filler assembly is proposed to address the issues of ineffective capacity utilization and inadequate cycling stability of high-energy-density cathode materials in solid-state lithium-ion batteries. It constructs a 3D interpenetrating charge-bridge network that effectively tackles the phase-separation challenge between fillers and electrolytes at the molecular level. Meanwhile, the molecular interlocking structure effectively inhibits the electrolyte erosion. More critically, it optimizes and stabilizes the cathode-electrolyte interface film, which facilitates the conduction of Li + -ions through a size-sieving mechanism. Consequently, this strategy enables effective adaptation across diverse high-energy-density cathode materials with satisfactory capacity performance (170.4 mAh g −1 at 4.5 V/1 C for LiNi 0.6 Co 0.2 Mn 0.2 O 2 and 194.0 mAh g −1 at 4.3 V/1 C for LiNi 0.9 Co 0.08 Mn 0.02 O 2 ). In conclusion, this investigation offers a straightforward and effective reference for addressing the critical challenges of ionic transport and interface stabilization in the design of gel electrolytes.

cathode-electrolyte interface↗

Linking DSC/TGA to Cell Levels: Energetics, Evolved Gases, and Thermal Safety of NMC811‐Graphite Micro‐Cell

Thermochemical characterization of battery materials links intrinsic material properties to decomposition pathways, heat generation, and gas evolution that govern performance and safety. Despite extensive work on NMC811-Graphite, variability across partial configurations and the limited adoption of micro-cell architectures (cathode+anode+electrolyte+separator) hinder robust cell-scale interpretation. Accordingly, this work establishes a bottom-up, component-resolved methodology integrating DSC/TGA, evolved gas analysis (EGA), and in situ XRD to link decomposition pathways and energy release across partial and micro-cell configurations, providing a transferable assessment of safety and stability in emerging chemistries. In separator-free configurations, the gas–solid reaction between cathode-evolved O 2 and anode-leached Li dominates the net heat release (1139 J g −1 ). In contrast, in the micro-cell configuration, the separator hinders O 2 transport and alters the timing and pathways of other reactions, and reduces the net energy release to 618 J g −1 . Energy release was organized into defined temperature windows that provide a framework for a thermodynamic model combining quantified gas evolution with selected decomposition pathways and effective reaction enthalpies to estimate net specific energy release, with agreement between DSC and cell-level tests. Ex situ XPS of heat-treated samples extends post-mortem analysis to thermal-abuse regimes, supporting key pathway elements.

25 ENERGY STORAGE↗

Design and optimization of processes for recovering rare earth elements from end‐of‐life permanent magnets

Recovery of rare earth elements (REEs) from end-of-life (EOL) products represents a strategic opportunity to strengthen the domestic supply chain for rare earth elements. This work presents a superstructure-based optimization framework for finding the most economical processing pathway for different EOL rare earth permanent magnets (REPMs). The framework evaluates state-of-the-art technologies across four processing stages—disassembly, demagnetization, leaching and extraction, and precipitation and calcination—using net present value (NPV) maximization and cost of recovery (COR) minimization objectives. A novel bottom-up costing framework for hydrogen decrepitation is also introduced. Two feedstocks were considered: REPMs from EOL hard disk drives (HDDs), and electric and hybrid electric vehicles (EVs and HEVs). While HDD recycling proved unprofitable due to limited feedstock availability, EVs/HEVs were profitable across a range of parameters and cost estimates. Therefore, our findings suggest that the proposed EOL EV/HEV recycling process may be economical and is worthy of further investigation.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Generation and Stabilization of a Dinickel Catalyst in a Metal-Organic Framework for Selective Hydrogenation Reactions

Although many monometallic active sites have been installed in metal–organic frameworks (MOFs) for catalytic reactions, there are no effective strategies to generate bimetallic catalysts in MOFs. Here we report the synthesis of a robust, efficient, and reusable MOF catalyst, MOF-NiH, by adaptively generating and stabilizing dinickel active sites using the bipyridine groups in MOF-253 with the formula of Al(OH)(2,2'-bipyridine-5,5'-dicarboxylate) for Z -selective semihydrogenation of alkynes and selective hydrogenation of C=C bonds in α,β-unsaturated aldehydes and ketones. Spectroscopic studies established the dinickel complex (bpy∙ - )Ni II ( μ 2 -H) 2 Ni II (bpy∙ - ) as the active catalyst. MOF-NiH efficiently catalyzed selective hydrogenation reactions with turnover numbers of up to 192 and could be used in five cycles of hydrogenation reactions without catalyst leaching or significant decrease of catalytic activities. The present work uncovers a synthetic strategy toward solution-inaccessible Earth-abundant bimetallic MOF catalysts for sustainable catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bio‐based glycerol plasticizers for flexible poly(vinyl chloride) blends

Abstract A series of glycerol‐based compounds were investigated for their application as plasticizers for flexible poly(vinyl chloride) (PVC) blends. The effect of plasticizer chemical structure on the performance, migration behavior, and blend morphology were evaluated and compared to blends produced using the commercial plasticizer dioctyl terephthalate (DOTP). Blends containing 40 phr (parts per hundred rubber) of glycerol‐based plasticizer showed a considerable reduction (between 54 to 86°C) in glass transition temperature ( T g ) relative to neat PVC ( T g ~ 80°C). Tensile testing of samples prepared with the glycerol analogs demonstrated higher ductility (elongation at break values of up to 97%) than DOTP (elongation at break value of 75%) at identical plasticizer loadings. The surface morphologies showed excellent incorporation of the glycerol plasticizers functionalized with alkyl chains longer than four carbons in length into the PVC matrix, whereas droplet formation was observed in blends with shorter chain glycerol derivatives. Leaching behavior of the plasticized samples were evaluated into different media and showed that plasticizers comprised of branched, or longer alkyl chains produced 2‐ to 4‐fold lower migration rates compared to those with shorter alkyl chains into polar solutions.

Halloran, Matthew W.↗

Nitrate Radical Facilitates Indirect Benzyl Alcohol Oxidation on Bismuth(III) Vanadate Photoelectrodes

Bismuth(III) vanadate (BiVO 4 ) films show activity for direct benzyl alcohol (PhCH 2 OH) oxidation to benzaldehyde (PhCHO) in acetonitrile solvent. Introducing tetrabutylammonium nitrate (Bu 4 NNO 3 ) drastically reduces the overpotential required to generate the PhCHO product while maintaining a high faradaic efficiency (FE) >90%. BiVO 4 corrosion accompanies PhCH 2 OH oxidation. However, the presence of nitrate ions (NO 3 - ) results in significantly less bismuth- and vanadium-ion leaching (determined by ICP-MS analysis), as well as reduced surface roughening (determined by SEM imaging). In this reaction, it is proposed that rate-determining NO 3 - oxidation generates a highly reactive nitrate radical (NO 3 ∙) that reacts with PhCH 2 OH by hydrogen-atom abstraction (HAT). NO 3 - is stoichiometrically consumed by the irreversible formation of electrochemically inert HNO 3 , characterized by an EC i mechanism, rather than a catalytic EC' mechanism. In the presence of PhCH 2 OH, NO 3 - oxidation on BiVO 4 becomes more facile; every order of magnitude increase in PhCH 2 OH concentration shifts the NO 3 - / NO 3 ∙ equilibrium potential negatively by 200 mV. The shift results from the introduction of a consumption pathway for the nitrate radical intermediate via a coupled chemical step with benzyl alcohol. This report is the first example of photoelectrochemical NO 3 ∙ generation to initiate indirect PhCH 2 OH oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phosphate‐functionalized Zirconium Metal–Organic Frameworks for Enhancing Lithium–Sulfur Battery Cycling

Abstract Lithium–sulfur batteries are promising candidates for next‐generation energy storage devices due to their outstanding theoretical energy density. However, they suffer from low sulfur utilization and poor cyclability, greatly limiting their practical implementation. Herein, we adopted a phosphate‐functionalized zirconium metal–organic framework (Zr‐MOF) as a sulfur host. With their porous structure, remarkable electrochemical stability, and synthetic versatility, Zr‐MOFs present great potential in preventing soluble polysulfides from leaching. Phosphate groups were introduced to the framework post‐synthetically since they have shown a strong affinity towards lithium polysulfides and an ability to facilitate Li ion transport. The successful incorporation of phosphate in MOF‐808 was demonstrated by a series of techniques including infrared spectroscopy, solid‐state nuclear magnetic resonance spectroscopy, and X‐ray pair distribution function analysis. When employed in batteries, phosphate‐functionalized Zr‐MOF (MOF‐808‐PO4) exhibits significantly enhanced sulfur utilization and ion diffusion compared to the parent framework, leading to higher capacity and rate capability. The improved capacity retention and inhibited self‐discharge rate also demonstrate effective polysulfide encapsulation utilizing MOF‐808‐PO4. Furthermore, we explored their potential towards high‐density batteries by examining the cycling performance at various sulfur loadings. Our approach to correlate structure with function using hybrid inorganic–organic materials offers new chemical design strategies for advancing battery materials.

Liu, Bingqian↗

Amphilic Water-Lean Carbon Capture Solvent Wetting Behavior through Decomposition by Stainless-Steel Interfaces

In this work, we report on a combined experimental and theoretical study of the wetting and reactivity of water-lean carbon capture solvents on the surface of common column packing materials. Paradoxically, we find that these solvents are equally able to wet hydrophobic and hydrophilic surfaces. The solvents are amphiphilic and are able to adapt to any interfacial environment due to their inherent heterogeneous molecular structure. Ab initio molecular dynamics indicates that these structures enable the formation of a strong adlayer on the surface of hydrophilic surfaces like oxidized steel which promotes solvent decomposition akin to hydrolysis from surface oxides and hydroxides. This decomposition passivates the surface, making it effectively hydrophobic, and the decomposed solvent promotes leaching of the iron into the bulk fluid. This study links the wetting behavior to the observed corrosion of the steels via decomposition of solvent at steel interfaces. The overall affect is strongly dependent on the chemical composition of the solvent, in that amines are stable, whereas imines and alcohols are not. We also observed that plastic packing shows little to no solvent degradation, but an equal degree of wetting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Progress on Photo‐, Electro‐, and Photoelectro‐Catalytic Conversion of Recalcitrant Polyethylene, Polypropylene, and Polystyrene ‐ A Review

Abstract Recalcitrant waste plastics such a polyethylene, polypropylene, and polystyrene are difficult to recycle and are mostly disposed of in landfills and eventually leached into the environmental as micro‐ and nano‐plastics. This review explores how photo‐, electro‐, and combined photoelectro‐catalytic processes can assist in the degradation and upcycling of waste plastic into different chemicals and mitigate their release to the environment. In this work, we discuss how the different reaction mechanisms proceed, explore the current relevant literature, and highlight the developments needed to advance the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nitrification, denitrification, and competition for soil N : Evaluation of two Earth System Models against observations

Abstract Earth System Models (ESMs) have implemented nitrogen (N) cycles to account for N limitation on terrestrial carbon uptake. However, representing inputs, losses, and recycling of N in ESMs is challenging. Here, we use global rates and ratios of key soil N fluxes, including nitrification, denitrification, mineralization, leaching, immobilization, and plant uptake (both NH 4 + and NO 3 − ), from the literature to evaluate the N cycles in the land model components of two ESMs. The two land models evaluated here, E3SM Land Model version 1 (ELMv1)‐ECA and CLM5.0, originated from a common model but have diverged in their representation of plant–microbe competition for soil N. The models predict similar global rates of gross primary productivity (GPP) but have approximately two‐fold to three‐fold differences in their underlying global mineralization, immobilization, plant N uptake, nitrification, and denitrification fluxes. Both models dramatically underestimate the immobilization of NO 3 − by soil bacteria compared with literature values and predict dominance of plant uptake by a single form of mineral nitrogen (NO 3 − for ELM, with regional exceptions, and NH 4 + for CLM5.0). CLM5.0 strongly underestimates the global ratio of gross nitrification:gross mineralization and both models are likely to substantially underestimate the ratio of nitrification:denitrification. Few experimental data exist to evaluate this last ratio, in part because nitrification and denitrification are quantified using different techniques and because denitrification fluxes are difficult to measure at all. More observational constraints on soil nitrogen fluxes such as nitrification and denitrification, as well as greater scrutiny of the functional impact of introducing separate NH 4 + and NO 3 − pools into ESMs, could help to improve confidence in present and future simulations of N limitation on the carbon cycle.

Nevison, Cynthia↗

Diversifying and perennializing plants in agroecosystems alters retention of new C and N from crop residues

Abstract Managing soils to retain new plant inputs is key to moving toward a sustainable and regenerative agriculture. Management practices, like diversifying and perennializing agroecosystems, may affect the decomposer organisms that regulate how new residue is converted to persistent soil organic matter. Here we tested whether 12 years of diversifying/perennializing plants in agroecosystems through extended rotations or grassland restoration would decrease losses of new plant residue inputs and, thus, increase retention of carbon (C) and nitrogen (N) in soil. We tracked dual‐labeled ( 13 C and 15 N), isotopically enriched wheat ( Triticum aestivum ) residue in situ for 2 years as it decomposed in three agroecosystems: maize–soybean (CS) rotation, maize–soybean–wheat plus red clover and cereal rye cover crops (CSW2), and spring fallow management with regeneration of natural grassland species (seven to 10 species; SF). We measured losses of wheat residue (C wheat and N wheat ) in leached soil solution and greenhouse gas fluxes, as well as how much was recovered in microbial biomass and bulk soil at 5‐cm increments down to 20 cm. CSW2 and SF both had unique, significant effects on residue decomposition and retention dynamics that were clear only when using nuanced metrics that able to tease apart subtle differences. For example, SF retained a greater portion of C wheat in 0–5 cm surface soils (155%, p = 0.035) and narrowed the C wheat to N wheat ratio ( p < 0.030) compared to CS. CSW2 increased an index of carbon‐retention efficiency, C wheat retained in the mesocosm divided by total measured, from 0.18 to 0.27 (49%, p = 0.001), compared to CS. Overall, we found that diversifying and extending the duration of living plants in agroecosystems can lead to greater retention of new residue inputs in subtle ways that require further investigation to fully understand.

McDaniel, Marshall D.↗

Directly Spun Epoxy-Crosslinked Polyethylenimine Fiber Sorbents for Direct Air Capture and Postcombustion Capture of CO 2

A novel, directly injected solid fiber sorbent is synthesized from a solvent-stable, epoxy-crosslinked basic immobilized amine sorbent (BIAS) for CO 2 capture. Leach resistance of the BIAS organics toward 1-methyl-2-pyrrolidone/H 2 O (90/10, fiber solvent) reaches near 100% at the expense of CO 2 capture and is achieved by increasing the extent of crosslinking. The optimized fiber sorbent, prepared with an N,N-diglycidyl-4-glycidyloxyaniline/polyethylenimine (PEI)-0.35/1 wt. ratio, retains 79.2% of PEI and captures 0.37 (direct air capture [DAC]) and 0.67 (postcombustion) mmol CO 2 g-fiber -1 . A nonoptimized prototype hollow fiber exhibits a stable 0.2 mmol CO 2 g-fiber -1 during DAC cycling and is assembled into a ten-fiber module. In conclusion, these results demonstrate a large step toward practical application of this material.

42 ENGINEERING↗

The channel-source hypothesis: Empirical evidence for in-channel sourcing of dissolved organic carbon to explain hysteresis in a headwater mountain stream

Catchment hydrologists have long puzzled over the question: How can catchments rapidly generate storm flows and pulses of solutes in response to storm events? Conceptual models viewing catchments as composed of discrete source areas generating flow at unique time scales and with unique chemical characteristics have been used to explain the observed changes in flow and water chemistry. Surprisingly, those conceptual models usually do not treat the stream channel as one of the potential source areas. We propose the channel-source hypothesis in which the stream itself should be considered as a potential source with the same rigour as other contributing areas. We pose this in the spirit of the scientific use of the word: a hypothesis is not a proven idea but rather a provisional supposition serving as the basis for further study. We suggest that the channel should be considered as a potential source for dissolved organic carbon (DOC). Channels store substantial amounts of organic matter, and stream ecologists have long studied stream carbon cycling. From those studies, we know that leaching and decomposition can generate DOC from particulate organic carbon (POC). Further, POC is stored in channel ‘dead-zones’—regions of low flow velocity - that can be activated as flow velocity increases, thus releasing accumulated DOC during storms. All catchments are different; there is no reason to assume that channel sources are always important, in every catchment, in every storm. Thus, the channel-source hypothesis does not replace existing conceptual models. Instead, it adds another potential mechanism that may explain DOC dynamics observed in streams. The channel-source hypothesis has substantial implications for catchment studies examining sources of DOC in stream water or using DOC as a tracer to determine the locations of, and proportional contributions of, different source areas for streamflow generation.

54 ENVIRONMENTAL SCIENCES↗

Recycling Perspectives of Electric Arc Furnace Slag in the United States: A Review

This article presents a comprehensive review of electric arc furnace (EAF) slag recycling in the United States, examining its classification and the associated challenges and opportunities of its industrial use. The study affirms EAF slag's nonhazardous status. Here, the main challenges identified in EAF slag applications include substantial variations in composition and volume instability during/after hydration. Analysis of the U.S. recycling practices reveals that EAF slag is predominantly reused, with minimal landfill disposal. However, its prevalent use as a low value-added aggregate in construction applications underscores the industry's ongoing challenge to get additional value from EAF slag recycling. Despite these challenges, the study highlights a great potential for increased value extraction from EAF slag recycling. Beyond conventional applications as a clinker material for the cement industry, the review explores modern technologies for steelmaking slag recycling, revealing options for recovering valuable metals such as Cr, V, Mo, and Fe through methods such as leaching, reduction, and oxidation.

42 ENGINEERING↗

Speciation and diffusive dynamics in hydrated grain boundaries of complex oxide Gd2Ti2O7

Abstract Grain boundaries in polycrystalline materials significantly affect their properties, such as ionic transport, corrosion, and chemical durability. The pyrochlore compound (Gd 2 Ti 2 O 7 ) is employed as a model for complex oxides and is known for its diverse applications, including nuclear waste immobilization. Density functional theory-based first-principles molecular dynamics simulations were performed at different temperatures on the hydrated grain boundary system. The results show extensive transformations within the grain boundaries among hydrous water species (OH − , H 2 O, and H 3 O + ). The temperature dependence of self-diffusion coefficients follows Arrhenius behavior, with an activation energy of 35.9 kJ/mol for hydrogen and 46.3 kJ/mol for oxygen. The lifetime of OH − is about three to four times longer than that of H 2 O at temperatures from 800 to 2100 K, suggesting the greater stability of OH − over H 2 O, a unique characteristic of the grain boundaries. The estimated lifetime of the hydrous species decreases as the temperature increases, with an activation energy of 9.9 kJ/mol for OH − and 13.4 kJ/mol for H 2 O. While Gd 3 + is more mobile than Ti 4+ , both the Gd 3 + and Ti 4+ cations are orders of magnitude less mobile than the water species. The results suggest that water species are much more mobile within grain boundaries than in the bulk crystal and have the potential to penetrate deep into polycrystalline materials through grain boundaries, leading to grain boundary degradation and dissolution. The different mobilities of cations in complex oxides can lead to leaching of certain cations and incongruent dissolution during the chemical weathering of Earth and industrial materials.

B. Ghosh, Dipta↗

Manganese uptake by red maples in response to mineral dissolution rates in soil

Manganese (Mn) is an essential plant micronutrient that influences photosynthesis, ecosystem productivity, and soil carbon storage. Our objective was to quantify how Mn uptake by forest vegetation relates to Mn release into soil solution through mineral dissolution. In this work, a greenhouse pot experiment was conducted to quantify Mn uptake by red maple saplings as a function of mineral solubility to test whether Mn uptake was limited by the supply of Mn to soil solution. Differences in soil microbial community composition between treatments, particularly amongst Mn cycling bacteria and fungi, were also evaluated to assess potential microbial impacts on observed Mn fluxes. Plant Mn uptake was highest in systems supplied with dissolved Mn(II) because it was not kinetically limited by mineral weathering. Mn uptake was also higher in systems supplied with a fast-weathering substrate (shale containing Mn(II)-bearing pyrite) than a slow-weathering substrate (Mn(IV)-oxide). However, vegetation accumulated a decreasing proportion of available Mn with increasing solubility, indicating that uptake was tempered relative to solubility. The presence of bacterial phyla containing known Mn-oxidizing bacteria indicates the potential for Mn-oxidizing bacteria to influence Mn solubility within Mn-oxide and dissolved Mn treatments. A relatively low abundance of these bacteria points to their limited capacity to oxidize and retain Mn in the shale treatments, consistent with substantial Mn leaching. We conclude that Mn uptake was primarily controlled by dissolution rates of Mn-bearing minerals but modified by biological processes. The quantitative framework presented here can guide understanding of how biogeochemical processes control element cycling between plants and soils.

59 BASIC BIOLOGICAL SCIENCES↗