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At least 73 records · Page 4

Adsorbate-induced adatom formation on Au-Cu bimetallic alloys and its possible consequences for CO 2 electroreduction

The adsorbate-induced formation of sub-nanometer clusters on transition-metal single crystals observed in previous high-pressure microscopic studies hinted at the in-situ formation of unique active sites even on large nanoparticle catalysts. We propose that the adatom formation energy can be used as an energetic descriptor for the initial step toward the adsorbate-induced metal-cluster formation process. This descriptor can be efficiently computed using density functional theory (DFT) calculations and applied for screening and identification of metal catalysts where this phenomenon may play an important role in generating active sites in-situ. As a proof of concept, here, we construct an adatom formation energy database for three Au x Cu y alloys (x:y = 3:1, 1:1, or 1:3) and eighteen adsorbates (H, C, N, O, F, S, Cl, Br, I, CH x , NH x (x = 1 – 3), CO, NO, and OH) commonly involved in catalytic reactions. The energetics of adatom formation were examined in all cases where the (111) terrace, (211) step-edge, and (874) kink were the sources of the adatom. We demonstrate that the presence of an adsorbate could alter not only the energetics for adatom formation but also the elemental nature of the preferred adatom being formed. Using our database, we identified promising systems which favor adsorbate-induced adatom formation under near-ambient conditions. Specifically, CO-induced adatom formation on all three Au-Cu alloy surfaces could occur under CO 2 electroreduction (CO 2 RR) conditions. This phenomenon offers a qualitative explanation for the experimentally observed CO 2 RR activity on Au-Cu alloy catalysts. As a result, our methodology offers an easily expandable and efficient approach for large-scale catalyst screening with regards to adatom/cluster formation under reaction conditions and provides insight into the possible nature of active sites on alloy catalysts from a novel perspective.

Active site↗

Properties and device performance of BN thin films grown on GaN by pulsed laser deposition

Wide and ultrawide-bandgap semiconductors lie at the heart of next-generation high-power, high-frequency electronics. Here, in this paper, we report the growth of ultrawide-bandgap boron nitride (BN) thin films on wide-bandgap gallium nitride (GaN) by pulsed laser deposition. Comprehensive spectroscopic (core level and valence band x-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and Raman) and microscopic (atomic force microscopy and scanning transmission electron microscopy) characterizations confirm the growth of BN thin films on GaN. Optically, we observed that the BN/GaN heterostructure is second-harmonic generation active. Moreover, we fabricated the BN/GaN heterostructure-based Schottky diode that demonstrates rectifying characteristics, lower turn-on voltage, and an improved breakdown capability (~234 V) as compared to GaN (~168 V), owing to the higher breakdown electrical field of BN. Our approach is an early step toward bridging the gap between wide and ultrawide-bandgap materials for potential optoelectronics as well as next-generation high-power electronics.

42 ENGINEERING↗

Data-Driven Art

In Fall 2023, Katie Baldwin (UAH) and Helen Parache (NASA) will follow up on their pilot activity from the spring that focused on collaboration between the arts and sciences at the UAH Art Department. Ms. Parache will present on open access data and artists that incorporate scientific data in their work, e.g. Tali Weinberg and Sarah Bryant (University of Alabama). Ms. Baldwin will demonstrate printmaking and mark making techniques. The students in Ms. Baldwin’s Book Arts class will participate in a series of generative activities and engage with data to develop content. The focus on the Art Department stems from the importance of Art as a cultural pillar. Tapping into the communication and social relevance of art could be an avenue to pursue Environmental Justice goals of interest to NASA. A creative perspective on data can bring about creative questions and solutions. The workshop incorporates changes based on feedback from the spring workshop.

data science↗

Active Debris Removal - A Grand Engineering Challenge for the Twenty-First Century

The collision between Iridium 33 and Cosmos 2251 in 2009 underlined the potential of an ongoing collision cascade effect (the Kessler Syndrome ) in the near-Earth orbital debris environment. A 2006 NASA analysis of the instability of the debris population in the low Earth orbit (LEO, the region below 2000 km altitude) shows that the environment has reached a point where the debris population will continue to increase in the next 200 years, even without any future launches. The increase is driven by fragments generated via collisions among existing objects in LEO. In reality, the situation will be worse than this prediction because satellite launches will continue and unexpected major breakups may continue to occur. Mitigation measures commonly adopted by the international space community (such as the 25-year rule) will help, but will be insufficient to stop the population growth. To better preserve the near-Earth space environment for future generations, active debris removal (ADR) should be considered. The idea of active debris removal is not new. However, due to the monumental technical, resource, operational, legal, and political challenges associated with removing objects from orbit, it has not yet been widely considered feasible. The recent major breakup events and the environment modeling efforts have certainly reignited the interest in using active debris removal to remediate the environment. This trend is further highlighted by the National Space Policy of the United States of America, released by the White House in June 2010, where the President explicitly directs NASA and the Department of Defense to pursue research and development of technology and techniques, to mitigate and remove on-orbit debris, reduce hazards, and increase understanding of the current and future debris environment. A 2009 modeling study by the NASA Orbital Debris Program Office has shown that, in order to maintain the LEO debris population at a constant level for the next 200 years, an active debris removal of about five objects per year is needed. The targets identified for removal are those with the highest mass and collision probability products. Analyses from the study indicate that the majority of those objects are spent upper stages with masses ranging from 1 to more than 8 metric tons, residing in several altitude regions and concentrated in about 10 inclination bands. To remove five of those objects per year in a cost-effective manner truly represents a grand challenge in engineering and technology development. An end-to-end debris removal operation includes, in general terms, launches orbit rendezvous, precision tracking, stabilization (of the tumbling motion), capture, and deorbit of the targets. An ADR system deigned to remove a single object is not very cost-effective. Therefore, the repeatability of the removal system is almost a requirement. Some of the technologies involved in the ADR process do exist, but the difficulty is to make them more cost effective. Other technologies, such as ways to stabilize a massive tumbling upper stage and the capture mechanisms, are new and will require major innovative research and development efforts. This paper summarizes an updated assessment of the environment, including what needs to be done to control the population growth, and outlines the major engineering and technology challenges to carry out active debris removal to preserve the environment.

Liou, Jer-Chyi↗

Towards understanding the formation of internal fragments generated by collisionally activated dissociation for top-down mass spectrometry

Top-down mass spectrometry (TD-MS) generates fragment ions that returns information on the polypeptide amino acid sequence. In addition to terminal fragments, internal fragments that result from multiple cleavage events can also be formed. Traditionally, internal fragments are largely ignored due to a lack of available software to reliably assign them, mainly caused by a poor understanding of their formation mechanism. To accurately assign internal fragments, their formation process needs to be better understood. Here we applied a statistical method to compare fragmentation patterns of internal and terminal fragments of peptides and proteins generated by collisionally activated dissociation (CAD). Internal fragments share similar fragmentation propensities with terminal fragments (e.g., enhanced cleavages N-terminal to proline and C-terminal to acidic residues), suggesting that their formation follows conventional CAD pathways. Internal fragments should be generated by subsequent cleavages of terminal fragments and their formation can be explained by the well-known mobile proton model. Additionally, internal fragments can be coupled with terminal fragments to form complementary product ions that span the entire protein sequence. These enhance our understanding of internal fragment formation and can help improve sequencing algorithms to accurately assign internal fragments, which will ultimately lead to more efficient and comprehensive TD-MS analysis of proteins and proteoforms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Nonlinear Coupling of Electromagnetic Ion Cyclotron and Lower Hybrid Waves in the Ring Current Region: The Magnetic Storm May 1-7 1998

The excitation of lower hybrid waves (LHWs) is a widely discussed mechanism of interaction between plasma species in space, and is one of the unresolved questions of magnetospheric multi-ion plasmas. In this paper we present the morphology, dynamics, and level of LHW activity generated by electromagnetic ion cyclotron (EMIC) waves during the May 2-7, 1998 storm period on the global scale. The LHWs were calculated based on our newly developed self-consistent model that couples the system of two kinetic equations: one equation describes the ring current (RC) ion dynamic, and another equation describes the evolution of EMIC waves. It is found that the LHWs are excited by helium ions due to their mass dependent drift in the electric field of EMIC waves. The level of LHW activity is calculated assuming that the induced scattering process is the main saturation mechanism for these waves. The calculated LHWs electric fields are consistent with the observational data.

Khazanov, G. V.↗

The Nonlinear Coupling of Electromagnetic Ion Cyclotron and Lower Hybrid Waves in the Ring Current Region

The excitation of lower hybrid waves (LHWs) is a widely discussed mechanism of interaction between plasma species in space, and is one of the unresolved questions of magnetospheric multi-ion plasmas. In this paper we present the morphology, dynamics, and level of LHW activity generated by electromagnetic ion cyclotron (EMIC) waves during the May 2-7, 1998 storm period on the global scale. The LHWs were calculated based on a newly developed self-consistent model (Khazanov et. al., 2002, 2003) that couples the system of two kinetic equations: one equation describes the ring current (RC) ion dynamic, and another equation describes the evolution of EMIC waves. It is found that the LHWs are excited by helium ions due to their mass dependent drift in the electric field of EMIC waves. The level of LHW activity is calculated assuming that the induced scattering process is the main saturation mechanism for these waves. The calculated LHWs electric fields are consistent with the observational data.

Khazanov, G. V.↗

A Review of the Recent NASA Long-Term Orbital Debris Environment Projection and Active Debris Removal Modeling Activities

The NASA Orbital Debris Program Office (ODPO) developed a high fidelity debris evolutionary model, LEGEND (a LEO-to-GEO Environment Debris model), in 2004 to enhance its capability to better model the near-Earth environment. LEGEND can mimic the growth of the historical debris population and project it into the future based on user-defined scenarios. The first major LEGEND study concluded that even without any future launches, the LEO population would continue to increase due to mutual collisions among existing objects. In reality, the increase will be worse than this prediction because of ongoing satellite launches and unexpected major breakups. Even with a full implementation of the commonly-adopted mitigation measures, the LEO population growth is inevitable. To preserve the near-Earth environment for future generations, active debris removal (ADR) must be considered. A follow-up LEGEND ADR study was completed recently. The main results indicate that (1) the mass and collision probability of each object can be used to establish an effective removal selection criterion and (2) a removal rate of ~5 objects per year is sufficient to stabilize the LEO environment. Due to the limitation of removal techniques, however, different target selection criteria (in size, altitude, inclination, etc.) may be more practical. A careful evaluation of the effectiveness of different proposed techniques must be carried out to maximize the long-term benefit to the environment.

Liou, J.C.↗

Transient Structure Current Generated by the Activation of a Squib Device

Experimental measurements of the currents in pyro-activation circuits show that a structure current is generated during the pyro-activation process. This current is a transient current and is an intense source of electromagnetic interference. Analysis has indicated that the noise voltage induced on candidate victim circuits is sufficient to cause circuit upset and/or latchup. A survey of flight anomaly records has also correlated the occurrence of anomalies with the pyro-activation process. Detailed analyses, taking the spacecraft cabling configuration and circuit sensitivities into account, have shown that the structure current induced noise voltage could definitely be the cause of the anomalies. The threat of the structure current due to pyro-activation can be alleviated by isolating the pyro-activation circuit from ground and by proper arrangement of the cables in sensitive circuits.

pyrotechnic↗

Mission Operations with an Autonomous Agent

The Remote Agent (RA) is an Artificial Intelligence (AI) system which automates some of the tasks normally reserved for human mission operators and performs these tasks autonomously on-board the spacecraft. These tasks include activity generation, sequencing, spacecraft analysis, and failure recovery. The RA will be demonstrated as a flight experiment on Deep Space One (DSI), the first deep space mission of the NASA's New Millennium Program (NMP). As we moved from prototyping into actual flight code development and teamed with ground operators, we made several major extensions to the RA architecture to address the broader operational context in which PA would be used. These extensions support ground operators and the RA sharing a long-range mission profile with facilities for asynchronous ground updates; support ground operators monitoring and commanding the spacecraft at multiple levels of detail simultaneously; and enable ground operators to provide additional knowledge to the RA, such as parameter updates, model updates, and diagnostic information, without interfering with the activities of the RA or leaving the system in an inconsistent state. The resulting architecture supports incremental autonomy, in which a basic agent can be delivered early and then used in an increasingly autonomous manner over the lifetime of the mission. It also supports variable autonomy, as it enables ground operators to benefit from autonomy when L'@ey want it, but does not inhibit them from obtaining a detailed understanding and exercising tighter control when necessary. These issues are critical to the successful development and operation of autonomous spacecraft.

Pell, Barney↗

The use of ion mobility spectrometry and gas chromatography/mass spectrometry for the detection of illicit drugs on clandestine records

Illicit drug distribution has over the past decade grown tremendously from simple 'drug pushing' where drugs were distributed from poorly organized individuals to today's well organized and well financed drug cartels. This change to a more 'corporate-like' atmosphere has resulted in a greater use of record keeping to monitor the profits generated. The use of record keeping by drug distributors is not restricted to high level drug smugglers but is used at all levels within the distribution network. Dealers at all levels including street dealers are generally 'fronted', given on consignment quantities of drugs that they in turn sell to customers, thereby requiring the need for records to keep track of drug sales versus liabilities. These records because of their illicit nature are often encrypted to hide the fact that they are indeed records of drug transactions. The creation of a handwritten notation concerning a drug transaction is normally brought on because of a purchase or sale. In a sale, this is commonly accomplished through a consignment, or the designation of a quantity to a customer to whom that amount has been 'fronted'. Because this activity generates a debt, it follows that an accounting for payments made, as well as new transactions completed, is only logical. One of the most common means of representing these is through an 'accounting flow', in which payments are subtracted from a running balance while new sales are added to it. The examination of illicit drug records has been the key to the prosecution of numerous federal, state, and local drug cases for a number of years. The Document Section of the FBI Laboratory, through its Racketeering Records Analysis Unit (RRAU), has been involved in such analytical efforts since 1983. Detailed analytical research brought about an evolution in the systematic approach utilized in the RRAU since that time. The close proximity of the drugs to the records often results in trace drug evidence being transferred to the records. The detection of trace drug residue on surfaces by ion mobility spectrometry (IMS) is well documented in literature. The following procedure will deal primarily with the newer techniques of trace drug analysis and drug record analysis developed by the Chemistry/Toxicology Unit of the FBI Laboratory since the more traditional techniques of latent finger print analysis and document analysis are well known.

Donnelly, Brian↗

Lidar Monitoring of Mexico City's Atmosphere During High Air Pollution Episodes

Over the last two decades, Mexico City, like many large industrial and populous urban areas, has developed a serious air pollution problem, especially during the winter months when there are frequent temperature inversions and weak winds. The deteriorating air quality is the result of several factors. The basin within which Mexico City lies in Mexico's center of political, administrative and economic activity, generating 34 percent of the gross domestic product and 42 percent of the industrial revenue, and supporting a population which is rapidly approaching the 20 million mark. The basin is surrounded by mountains on three sides which end up preventing rapid dispersal of pollutants. Emissions from the transportation fleet (more than 3 million vehicles) are one of the primary pollution sources, and most are uncontrolled. Catalytic converters are just now working their way into the fleet. The Mexico City Air Quality Research Initiative in an international collaboration project between the Los Alamos National Laboratory and the Mexican Petroleum Institute are dedicated to the investigation of the air quality problem in Mexico City. The main objective of the project is to identify and assess the cost and benefits of major options being proposed to improve the air quality. The project is organized into three main activity areas: (1) modeling and simulation; (2) characterization and measurements; and (3) strategic evaluation.

Quick, C. R., Jr.↗

Idaho National Laboratory Integrated Multisite SSHAC Level 3: Probabilistic Volcanic Hazards Assessment

The Idaho National Laboratory (INL) resides on the eastern Snake River Plain (ESRP), part of the Snake River Plain (SRP) with a complex origin and geologic history of volcanism. Much of the Quaternary (last 2.58 million years) volcanism within 400 km of INL is genetically associated with a major thermal anomaly referred to as the Yellowstone hotspot, which is currently located more than 180 km northeast of INL. Near INL, local volcanic sources include silicic domes near its southern border, and numerous dike-fed basaltic vents of the ESRP, some of which are near or within the INL boundaries. Quantitative probabilistic assessments of screened-in volcanic hazardous phenomena for nine different facility complexes at the INL are presented for a Senior Seismic Hazard Analysis Committee (SSHAC) Level 3 (SL3) study. The comprehensive, integrated multisite SSHAC study consists of a single regional Probabilistic Volcanic Hazards Assessment (PVHA) that pertains to all nine INL facility complexes, with site-specific information developed at each respective area of interest (AOI), referred to as the "INL facility AOI" (Figure ES-1). Hazard products are generated for specified INL facility AOIs for use by multiple stakeholders from different agencies in risk-informed decision-making regarding site selection, operations, and design of nuclear facilities at INL, consistent with U.S. Department of Energy (DOE) and U.S. Nuclear Regulatory Commission (NRC) regulatory guidance. The study also serves as the basis for future periodic safety assessments required for existing DOE facilities, such as 10-year evaluations of natural-phenomena hazards. Elements of the INL PVHA including initial characterization, screening, quantitative assessments of eruption and hazard potential, and consideration of facility needs are conducted using the three phases of the SSHAC process: evaluation, integration, and documentation. As per regulatory guidance, the SSHAC framework provided the necessary processes and procedures for the PVHA Technical Integration (TI) team, at three workshops, five formal working meetings and many TI team remote meetings, to conduct initial characterization, screen the volcanic hazards, create PVHA model inputs, exercise those models in the PVHA, consider facility-specific volcanic hazard needs, and perform final hazard calculations. The Participatory Peer Review Panel (PPRP) provided independent oversight and performed process and technical reviews of the PVHA throughout its duration. The study included an extensive New Data Collection and Analyses (NDCA) program developed by the PVHA TI team to reduce uncertainties in hazard-significant elements in the PVHA model. NDCA activities generated 20 reports providing important contributory datasets and results to the project database for characterizing the ESRP. For example, a report compiling the dimensions of ESRP shield volcanoes and lava fields was used to construct volcanic footprints (areas of impact), was compared with data from INL subsurface cores, and was used to validate the results of lava-flow inundation modeling on the contemporary terrain. Another example is the acquisition of aeromagnetic data over INL and its surrounding area, with maps of buried magmatic features (e.g., subsurface volcanoes and swarms of feeder dikes) that informed the PVHA conceptual model of volcanism. The SSHAC evaluation process was used to conduct all elements of the PVHA including initial characterization and screening. Existing data and NDCA activities provided the foundation to develop the tectonomagmatic conceptual model of volcanism for the region of geographical interest in the SRP and Yellowstone hotspot volcanic system, and for considering volcanoes in the western US. Considering Quaternary volcanic sources active during this period, the screening approach identified and evaluated magma compositions, types of eruptive and intrusive phenomena, types of hazardous phenomena, and proximity of sources to INL. The PVHA TI team evaluated 18 types of magmatic sources in terms of 20 potentially hazardous phenomena, resulting in 360 screening decisions. The screening process resulted in 140 screened-in hazardous volcanic phenomena for Quaternary volcanic sources 1) proximal to INL facility complexes in the ESRP (64 basaltic and 54 silicic), 2) regional sources associated with the Yellowstone caldera system and Blackfoot Reservoir volcanic field (7), and 3) more distal sources from thirteen Cascade volcanoes and two volcanoes at Long Valley caldera (CA).

58 GEOSCIENCES↗

Oxidative Grafting for Catalyst Synthesis in Surface Organometallic Chemistry

The development of new methods of catalyst synthesis with the potential to generate active site structures orthogonal to those accessible by traditional protocols is of great importance for discovering new materials for addressing challenges in the evolving energy and chemical economy. Here, in this work, the generality of oxidative grafting of organometallic and well-defined molecular metal precursors onto redox-active surfaces such as manganese dioxide (MnO 2 ) and lithium manganese oxide (LiMn 2 O 4 ) is investigated. Nine molecular metal precursors are explored, spanning groups 4–11 and each of the three periods of the transition metal series. The byproducts of the oxidative grafting reaction, a mixture of protodemetalation and ligand homocoupling for several organometallic precursors, was found to provide insights into the mechanism of the grafting reaction, suggesting oxidation of both the metal d-orbitals, as well as the metal–carbon σ-bonds, resulting in ejection of the ligand radical fragment. Analysis of the supported structures and oxidation state by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) suggests that several of the chemisorbed metal ions are intercalated into interstitial vacancies of the surface structure while other complexes form intact molecular fragments on the surface. Proof of concept for the use of this metalation protocol to generate diverse, metal-dependent catalytic performance is demonstrated by the application of these materials in the conversion of cyclohexane to K/A oil (cyclohexanol and cyclohexanone) with tert-butyl hydroperoxide, as well as in the low-temperature (T ≤ 50 °C) oxidation of carbon monoxide to carbon dioxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Balance in a rotating artificial gravity environment

When subjects stand at the center of a fully enclosed room that is rotating at constant velocity, their natural postural sway generates Coriolis forces that destabilize their center of mass and head. We quantitatively assessed how exposure to constant velocity rotation at 10 rpm affected postural control. Twelve subjects stood in a heel-to-toe stance in the rotating room. Each test session involved three phases: (1) pre-rotation, (2) per-rotation, and (3) post-rotation. In each phase, subjects were tested in both eyes open and eyes closed conditions. Four measures were used to characterize center of mass movement and head movement: mean sway amplitude, total power, mean power frequency, and frequency of maximum power. Each measure was computed for anterior-posterior and medial-lateral sway. Both anterior-posterior and medial-lateral head and center of mass sway during rotation had significantly greater mean sway amplitude and total power compared with pre- and post-rotation values. Mean power frequency and frequency of maximum power were little affected. Eyes open conditions were significantly more stable in all test phases than eyes-closed, but vision did not completely suppress the effects of rotation. The greatest effect of rotation was in the eyes-closed condition with mean sway amplitude and total power increasing more than twofold. Inverted pendulum sway was maintained in all phases of both test conditions. No aftereffects of rotation were present after the four 25-s exposures each subject received. We expect that with longer exposure periods and with active generation of body sway subjects would both adapt to rotation and exhibit post-rotary aftereffects.

NASA Discipline Neuroscience↗

Evaluation of SNOLAB background mitigation procedures through the use of an ICP-MS based dust monitoring methodology

Dust particulate fallout on materials in use for rare-event searches is a concerning source of radioactive backgrounds due to the presence of the naturally occurring radionuclides 40 K, 232 Th, 238 U, and their progeny in dust. Much effort is dedicated to inform radioactive backgrounds from dust and evaluate the efficacy of mitigation procedures. A great portion of such effort relies on fallout models and assumed dust composition. Here, in this work, an ICP-MS based methodology was employed for a direct determination of fallout rates of radionuclides and stable isotopes of interest from dust particulate at the SNOLAB facility. Hosted in an active mine, the SNOLAB underground laboratory strives to maintain experimental areas at class 2000 cleanroom level. This work validates the mitigation procedures in place at SNOLAB and informs dust backgrounds during laboratory activities. Fallout rates of major constituents of the local rock were measured two to three orders of magnitude lower in the clean experimental areas compared to non-clean transition areas from the mine to the laboratory. An increase of approximately two orders of magnitude in the fallout rate of stable Pb isotopes was determined in an experimental area during activities involving handling of Pb bricks. Increased 40 K, 232 Th, and 238 U fallout rates were measured in clean experimental areas during activities generating particulate.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Enabling high-throughput enzyme discovery and engineering with a low-cost, robot-assisted pipeline

Abstract As genomic databases expand and artificial intelligence tools advance, there is a growing demand for efficient characterization of large numbers of proteins. To this end, here we describe a generalizable pipeline for high-throughput protein purification using small-scale expression in E. coli and an affordable liquid-handling robot. This low-cost platform enables the purification of 96 proteins in parallel with minimal waste and is scalable for processing hundreds of proteins weekly per user. We demonstrate the performance of this method with the expression and purification of the leading poly(ethylene terephthalate) hydrolases reported in the literature. Replicate experiments demonstrated reproducibility and enzyme purity and yields (up to 400 µg) sufficient for comprehensive analyses of both thermostability and activity, generating a standardized benchmark dataset for comparing these plastic-degrading enzymes. The cost-effectiveness and ease of implementation of this platform render it broadly applicable to diverse protein characterization challenges in the biological sciences.

36 MATERIALS SCIENCE↗