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At least 271 records · Page 15

Selective Synthesis of a Series of Isostructural M II Cu I Heterobimetallic Complexes Spontaneously Assembled by an Unsymmetrical Naphthyridine‐Based Ligand

Abstract Metal–metal cooperation is integral to the function of many enzymes and materials, and model complexes hold enormous potential for providing insights into the capabilities of analogous multimetallic cores. However, the selective synthesis of heterobimetallic complexes still presents a significant challenge, especially for systems that hold the metals in close proximity and feature open or reactive coordination sites for both metals. To address this issue, a rigid, naphthyridine‐based dinucleating ligand featuring distinct binding environments was synthesized. This ligand enables the selective synthesis of a series of M II Cu I bimetallic complexes (M=Mn, Fe, Co, Ni, Cu, Zn), in which each metal center exclusively occupies its preferred binding pocket, from simple chloride salts. The precision of this selectivity is evident from cyclic voltammetry, ESI‐MS and anomalous X‐ray diffraction measurements.

Nicolay, Amélie↗

Implementation of Substructure Flexibility and Member-Level Load Capabilities for Floating Offshore Wind Turbines in OpenFAST

OpenFAST is an open-source, physics-based engineering tool applicable to the load analysis of land-based and offshore wind turbines, including floating offshore wind turbines. The substructure for a floating wind turbine has historically been modeled in OpenFAST as a rigid body with hydrodynamic loads lumped at a point, which enabled the tool to predict the global response of the floating substructure but not the structural loads within its individual members. This limitation is an impediment to designing floating substructures - especially newer designs that are more streamlined, flexible, and cost-effective. This paper presents the development of new functionality in OpenFAST to model floating substructure flexibility and member-level loads, as well as the concepts and mathematical background needed to understand and apply it correctly.

17 WIND ENERGY↗

A Glimpse into Photodetachment Spectra of Giant and Nested Fullerene Anions

We focus on the study of the photodetachment of bare, i.e., single-cage (CN)− as well as nested (multi-cage) (CN@CM@…)− singly charged fullerene anions. We calculate the attached electron’s wavefunctions, energies, oscillator strengths and photodetachment cross sections of the C60−, C240−, C540−, (C60@C240)−, (C60@C540)−, (C240@C540)− and (C60@C240@C540)− fullerene anions, where the attached electron is captured into the ground s-state by the resultant external field provided by all fullerene cages in the anion. The goal is to gain insight into the changes in behavior ofphotodetachment of this valence electron as a function of the different geometries and potentials of the various underlying fullerenes or nested fullerenes (fullerene onions) both due to their increasing size and due to “stuffing” of a larger bare fullerene with smaller fullerenes. To meet this goal, we opt for a simple semi-empirical approximation to this problem: we approximate each individual fullerene cage by a rigid potential sphere of a certain inner radius, thickness and potential depth, as in numerous other model studies performed to date. The results reveal a number of rather significant differences in the wavefunctions, oscillator strengths and photodetachment cross sections among these fullerene anions, some of which are completely counter-intuitive. The results obtained can serve as a “zeroth-order-touchstone” for future studies of single-cage and nested fullerene anions by more rigorous theories and/or experiments to build upon this work to assess the importance of interactions omitted in the present study.

Dolmatov, Valeriy K.↗

Conserving asphalt resources: Rethinking rejuvenator performance evaluation through peptizing efficiency

Timely rejuvenation and restoration of asphalt are essential conservation practices that help preserve and extend the service life of roads, bridges, driveways, and parking lots. The performance of asphalt rejuvenators is often assessed based on their diffusion rates and softening power, yet these metrics alone fail to capture true rejuvenation potential. Here, this study integrates density functional theory (DFT) modeling with experimental analysis to show that rejuvenation effectiveness is primarily governed by molecular interactions with oxidized asphaltene nanoaggregates. DFT results revealed that amide- and unsaturated-chain compounds, such as hexadecanamide, oleic acid, and 9,17-octadecadienal, act cooperatively to disrupt π–π stacking and exfoliate asphaltene layers, reducing binding strength and enhancing dispersion. Unlike bulky, rigid molecules that remain trapped, these components remain mobile and repeatedly interact with multiple aggregation sites. Experimental validation using rheometry and FTIR confirmed that such molecularly compatible rejuvenators restore the binder flexibility and polydispersity, even when diffusion is relatively slow. Building on this mechanistic foundation, six rejuvenators (A2, A5, A7, A8, A9, and A10) were evaluated using a three-metric performance framework encompassing cracking resistance (Glover–Rowe parameter), UV stability, and surface hydrophobicity. Among the six rejuvenators evaluated, A9 exhibited the highest overall performance, reducing the Glover–Rowe cracking parameter by 85% (from 351 kPa to 53 kPa), demonstrating the greatest resistance to UV-induced aging with a stability index of 4.17 h·kPa⁻¹, and increasing surface hydrophobicity to a contact angle of 103.6°. Its superior performance is primarily attributed to its amide- and unsaturated-chain components, which act cooperatively to disrupt π–π stacking interactions and exfoliate asphaltene layers, thereby promoting molecular deagglomeration and enhancing long-term durability. These results shift the criteria for selecting rejuvenators: effective candidates must pair the electronic capability to unlock aged asphaltenes with sufficient structural stability to resist secondary aging and restore hydrophobicity. Restoring hydrophobicity is critical, as aging reduces the asphalt’s water repellency and increases water diffusion, which in turn accelerates moisture-related damage; consequently, a high-performing rejuvenator must effectively restore the binder’s hydrophobic characteristic. Collectively, these findings provide a framework for the rational design of next-generation of bio-based rejuvenators that enhance pavement longevity and promote long-term sustainability.

Aging↗

Impedance-Based Detection of NO 2 Using Ni-MOF-74: Influence of Competitive Gas Adsorption

Chemically robust, low-power sensors are needed for the direct electrical detection of toxic gases. Metal–organic frameworks (MOFs) offer exceptional chemical and structural tunability to meet this challenge, though further understanding is needed regarding how coadsorbed gases influence or interfere with the electrical response. To probe the influence of competitive gases on trace NO 2 detection in a simulated flue gas stream, a combined structure–property study integrating synchrotron powder diffraction and pair distribution function analyses was undertaken, to elucidate how structural changes associated with gas binding inside Ni-MOF-74 pores correlate with the electrical response from Ni-MOF-74-based sensors. Data were evaluated for 16 gas combinations of N 2 , NO 2 , SO 2 , CO 2 , and H 2 O at 50 °C. Fourier difference maps from a rigid-body Rietveld analysis showed that additional electron density localized around the Ni-MOF-74 lattice correlated with large decreases in Ni-MOF-74 film resistance of up to a factor of 6 × 10 3 , observed only when NO 2 was present. These changes in resistance were significantly amplified by the presence of competing gases, except for CO 2 . Without NO 2 , H 2 O rapidly (<120 s) produced small (1–3×) decreases in resistance, though this effect could be differentiated from the slower adsorption of NO 2 by the evaluation of the MOF’s capacitance. Furthermore, samples exposed to H 2 O displayed a significant shift in lattice parameters toward a larger lattice and more diffuse charge density in the MOF pore. Evaluating the Ni-MOF-74 impedance in real time, NO 2 adsorption was associated with two electrically distinct processes, the faster of which was inhibited by competitive adsorption of CO 2 . Together, this work points to the unique interaction of NO 2 and other specific gases (e.g., H 2 O, SO 2 ) with the MOF’s surface, leading to orders of magnitude decrease in MOF resistance and enhanced NO2 detection. Finally, understanding and leveraging these coadsorbed gases will further improve the gas detection properties of MOF materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Helical Complex Ladder Polymer with Amplification of Asymmetry

Here, we report a Cu–salen helical complex ladder polymer (HLP-Cu) built from covalently fused Cu(Salen) units. Point chirality from enantiopure diamines directs the formation of a rigid, π-conjugated helix. Compared with a planar analogue (LLP-Cu) and the Cu(Salen) monomer, HLP-Cu exhibits up to 5-fold stronger circular dichroism and a maximum dissymmetry factor of 7.4 × 10 –3 . Titration experiments suggest a cooperative amplification of asymmetry arising from extended conjugation and helical geometry during helix formation. Time-dependent density functional theory calculations are employed to support this hypothesis, showing that increasing conjugation length and helical order enhance the rotational strength of contributing excited states via elevated magnetic transition moments and improved alignment of electric and magnetic transition moments. Our findings provide a new polymer platform for designing functional chiral materials with tunable chiroptical and spin-dependent properties.

36 MATERIALS SCIENCE↗

Physics augmented machine learning discovery of composition-dependent constitutive laws for 3D printed digital materials

Multi-material 3D printing, particularly through polymer jetting, enables the fabrication of digital materials by mixing distinct photopolymers at the micron scale within a single build to create a composite with tunable mechanical properties. Here, this work presents an integrated experimental and computational investigation into the composition-dependent mechanical behavior of 3D printed digital materials. We experimentally characterize five formulations, combining soft and rigid UV-cured polymers under uniaxial tension and torsion across three strain and twist rates. The results reveal nonlinear and rate-dependent responses that strongly depend on composition. To model this behavior, we develop a physics-augmented neural network (PANN) that combines a partially input convex neural network (pICNN) for learning the composition-dependent hyperelastic strain energy function with a quasi-linear viscoelastic (QLV) formulation for time-dependent response. The pICNN ensures convexity with respect to strain invariants while allowing non-convex dependence on composition. To enhance interpretability, we apply $L_0$ sparsification. For the time-dependent response, we introduce a multilayer perceptron (MLP) to predict viscoelastic relaxation parameters from composition. The proposed model accurately captures the nonlinear, rate-dependent behavior of 3D printed digital materials in both uniaxial tension and torsion, achieving high predictive accuracy for interpolated material compositions. This approach provides a scalable framework for automated, composition-aware constitutive model discovery for multi-material 3D printing.

Constitutive modeling↗

Entanglement Effect and Angular Momentum Conservation in a Nonseparable Tunneling Treatment

The important, and often dominant, role of tunneling in low temperature kinetics has resulted in numerous theoretical explorations into the methodology for predicting it. Nevertheless, there are still key aspects of the derivations that are lacking, particularly for nonseparable systems in the low temperature regime, and further explorations of the physical factors affecting the tunneling rate are warranted. In this work we obtain a closed-form rate expression for the tunneling rate constant that is a direct analog of the rigid-rotor-harmonic-oscillator expression. This expression introduces a novel "entanglement factor" that modulates the reaction rate. Furthermore, we are able to extend this expression, which is valid for nonseparable systems at low temperatures, to properly account for the conservation of angular momentum. In contrast, previous calculations have considered only vibrational transverse modes and so effectively employ a decoupled rotational partition function for the orientational modes. We also suggest a simple theoretical model to describe the tunneling effects in the vicinity of the crossover temperature (the temperature where tunneling becomes the dominating mechanism). This model allows one to naturally classify, interpret, and predict experimental data. Among other things, it quantitatively explains in simple terms the so-called "quantum bobsled" effect, also known as the negative centrifugal effect, which is related to curvature of the reaction path. Taken together, the expressions obtained here allow one to predict the thermal and E-resolved rate constants over broad ranges of temperatures and energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chloride Ion Transport by the E. coli CLC Cl – /H + Antiporter: A Combined Quantum-Mechanical and Molecular-Mechanical Study

We performed steered molecular dynamics (SMD) and umbrella sampling simulations of Cl – ion migration through the transmembrane domain of a prototypical E. coli CLC Cl – /H + antiporter by employing combined quantum-mechanical (QM) and molecular-mechanical (MM) calculations. The SMD simulations revealed interesting conformational changes of the protein. While no large-amplitude motions of the protein were observed during pore opening, the side chain rotation of the protonated external gating residue Glu148 was found to be critical for full access of the channel entrance by Cl – . Moving the anion into the external binding site (S ext ) induced small-amplitude shifting of the protein backbone at the N-terminal end of helix F. As Cl – traveled through the pore, rigid-body swinging motions of helix R separated it from helix D. Helix R returned to its original position once Cl – exited the channel. Population analysis based on polarized wavefunction from QM/MM calculations discovered significant (up to 20%) charge loss for Cl – along the ion translocation pathway inside the pore. The delocalized charge was redistributed onto the pore residues, especially the functional groups containing π bonds (e.g., the Tyr445 side chain), while the charges of the H atoms coordinating Cl – changed almost negligibly. Potentials of mean force computed from umbrella sampling at the QM/MM and MM levels both displayed barriers at the same locations near the pore entrance and exit. However, the QM/MM PMF showed higher barriers (~10 kcal/mol) than the MM PMF (~2 kcal/mol). Binding energy calculations indicated that the interactions between Cl – and certain pore residues were overestimated by the semi-empirical PM 3 Hamiltonian and underestimated by the CHARMM36 force fields, both of which were employed in the umbrella sampling simulations. In particular, CHARMM36 underestimated binding interactions for the functional groups containing π bonds, missing the stabilizations of the Cl – ion due to electron delocalization. The results suggested that it is important to explore these quantum effects for accurate descriptions of the Cl – transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Rest-frame Optical (900 nm) Galaxy Luminosity Function at z ∼ 4–7: Abundance Matching Points to Limited Evolution in the M{sub STAR}/M{sub HALO} Ratio at z ≥ 4

We present the first determination of the galaxy luminosity function (LF) at z ∼ 4, 5, 6, and 7, in the rest-frame optical at λ{sub rest}∼900 nm (z′ band). The rest-frame optical light traces the content in low-mass evolved stars (∼stellar mass—M {sub *}), minimizing potential measurement biases for M {sub *}. Moreover, it is less affected by nebular line emission contamination and dust attenuation, is independent of stellar population models, and can be probed up to z ∼ 8 through Spitzer/IRAC. Our analysis leverages the unique full-depth Spitzer/IRAC 3.6–8.0 μm data over the CANDELS/GOODS-N, CANDELS/GOODS-S, and COSMOS/UltraVISTA fields. We find that, at absolute magnitudes where M{sub z{sup ′}} is fainter than ≳−23 mag, M{sub z{sup ′}} linearly correlates with M{sub UV,1600}. At brighter M{sub z{sup ′}}, M{sub UV,1600} presents a turnover, suggesting that the stellar mass-to-light ratio M{sub ∗}/L{sub UV,1600} could be characterized by a very broad range of values at high stellar masses. Median-stacking analyses recover an M{sub ∗}/L{sub z{sup ′}} roughly independent on M{sub z{sup ′}} for M{sub z{sup ′}}≳−23 mag, but exponentially increasing at brighter magnitudes. We find that the evolution of the LF marginally prefers a pure luminosity evolution over a pure density evolution, with the characteristic luminosity decreasing by a factor of ∼5× between z ∼ 4 and z ∼ 7. Direct application of the recovered M{sub ∗}/L{sub z{sup ′}} generates stellar mass functions consistent with average measurements from the literature. Measurements of the stellar-to-halo mass ratio at fixed cumulative number density show that it is roughly constant with redshift for M{sub h}≳10{sup 12}M{sub ⊙}. This is also supported by the fact that the evolution of the LF at 4≲z≲7 can be accounted for by a rigid displacement in luminosity, corresponding to the evolution of the halo mass from abundance matching.

79 ASTRONOMY AND ASTROPHYSICS↗

Competitive Binding of Ethylene, Water, and Carbon Monoxide in Metal–Organic Framework Materials with Open Cu Sites

Typically, metal–organic frameworks (MOFs) with open metal sites (OMS) are understood to have selectivity in olefin/paraffin separations because of π–π interactions between olefin double bonds and OMS. One concern associated with these separations is that other species that potentially bind to OMS may also be present in feed streams, causing competition for these sites. We used density functional theory (DFT) to assess the binding energy of ethylene, water, and carbon monoxide on a set of more than 60 MOFs with open Cu sites in the form of Cu dimers. A useful observation from our results is that the relative binding energies of pairs of molecules (e.g., ethylene and water) can be calculated accurately from calculations that hold the MOF structure rigid and only relax the positions of the adsorbing molecules. These kinds of calculations are far more numerically efficient than calculations that relax all degrees of freedom in the system, so this observation will be useful in future efforts to screen larger collections of materials. A second observation is that the binding energies of each molecule in the 60 MOFs are quite similar to the binding energies in CuBTC, an exemplar MOF with open Cu sites in the form of Cu dimers. Analysis of the variations that do exist in the binding energies among materials points to possible avenues for controlling either the absolute binding energies or the relative binding energies of species associated with OMS in these materials. The third observation is that two unusual MOFs can bind ethylene more strongly than water because of a dual-site binding mechanism in which an ethylene molecule can interact simultaneously with both dimers while the smaller water molecule interacts primarily with a single OMS. This observation suggests a possible avenue for developing other MOFs in which the binding energy of ethylene is higher than that of water.

36 MATERIALS SCIENCE↗

Exponential Water Uptake in Ionomer Membranes Results from Polymer Plasticization

Water content is the most influential factor in the performance of ion-exchange membranes (IEMs), controlling their mechanical rigidity, ionic conductivity, and degradation rates. Membranes absorb water exponentially at high water activity (a w ), making that region of the sorption isotherm the most influential on membrane properties. Plasticization of the polymer by water has been proposed to cause this exponential uptake at high a w . However, an integrated microscopic picture of the structure, thermodynamic, and mechanical properties of IEMs as a function of a w has remained elusive. In this work, we use large-scale molecular simulations validated with experimental measurements to compute the sorption isotherms, Young’s modulus, polymer dynamics, and structure of IEMs. The simulations unveil that the exponential increase in water uptake (WU) coincides in all cases with the glass to rubber transition of the membrane, as measured through its Young’s modulus and segmental polymer dynamics. Functionalization of the polymer with alkyl groups further contributes to its plasticization, increasing the WU at a given a w and ion-exchange capacity (IEC). The alkyl chains act synergistically with water to plasticize the polymer matrix and allow water penetration in the membrane. The simulations reveal that the width of the water channels depends on the ratio λ of water to ions in the polymer but is independent of its IEC. We conclude that differences in the polymer matrix–not the water channels–are responsible for the distinct uptake response of IEMs to the thermodynamic driving force of water activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectral Element Modeling of Acoustic to Seismic Coupling Over Topography

Acoustic waves in the atmosphere are commonly recorded on seismometers as they couple into the ground. These signals, here called ground coupled airwaves, are not commonly considered in numerical modeling of infrasound propagation, which often assumes a rigid unmeshed boundary. Starting from an analytically-tractable spherical wave model, we analyze how the coupling of an acoustic wave into a planar elastic halfspace changes over a wide range of scenarios. We use energy admittance to quantify acoustic to seismic coupling over both a planar elastic halfspace and meshed topography. Our spectral element and analytic calculations have different maxima as a function of incidence angle, with very high admittance values for near-vertical incidence (maximum ≈78%). Energy admittance calculations at shallow incidence angles are much smaller (less than 1%). In simulations over the complex topography of Sakurajima Volcano, we attribute the variable spatial pattern of energy admittance to changes in earth parameters between each model. The observed pressure difference over the simulated 15 km region appears to be < 2%. While this value is relatively small, the cumulative addition over 100s of km and multiple acoustic bounce points may be significant. Acoustic to seismic coupling along the propagation path may bias long distance yield estimates, particularly when infrasound propagates over regions with steep topography or particularly slow seismic velocities, such as alluvial planes.

58 GEOSCIENCES↗

Multiscale porous elastomer substrates for multifunctional on-skin electronics with passive-cooling capabilities

In addition to mechanical compliance, achieving the full potential of on-skin electronics needs the introduction of other features. For example, substantial progress has been achieved in creating biodegradable, self-healing, or breathable, on-skin electronics. However, the research of making on-skin electronics with passive-cooling capabilities, which can reduce energy consumption and improve user comfort, is still rare. Herein, we report the development of multifunctional on-skin electronics, which can passively cool human bodies without needing any energy consumption. This property is inherited from multiscale porous polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) supporting substrates. The multiscale pores of SEBS substrates, with characteristic sizes ranging from around 0.2 to 7 µm, can effectively backscatter sunlight to minimize heat absorption but are too small to reflect human-body midinfrared radiation to retain heat dissipation, thereby delivering around 6 °C cooling effects under a solar intensity of 840 W∙m -2 . Other desired properties, rooted in multiscale porous SEBS substrates, include high breathability and outstanding waterproofing. The proof-of-concept bioelectronic devices include electrophysiological sensors, temperature sensors, hydration sensors, pressure sensors, and electrical stimulators, which are made via spray printing of silver nanowires on multiscale porous SEBS substrates. The devices show comparable electrical performances with conventional, rigid, nonporous ones. Also, their applications in cuffless blood pressure measurement, interactive virtual reality, and human–machine interface are demonstrated. Notably, the enabled on-skin devices are dissolvable in several organic solvents and can be recycled to reduce electronic waste and manufacturing cost. Such on-skin electronics can serve as the basis for future multifunctional smart textiles with passive-cooling functionalities.

42 ENGINEERING↗

Structural and Biophysical Properties of a [4Fe-4S] Ferredoxin-Like Protein from Synechocystis sp. PCC 6803 with a Unique Two Domain Structure

Electron carrier proteins (ECPs), binding iron-sulfur clusters, are vital components within the intricate network of metabolic and photosynthetic reactions. They play a crucial role in the distribution of reducing equivalents. In Synechocystis sp. PCC 6803, the ECP network includes at least nine ferredoxins. Previous research, including global expression analyses and protein binding studies, has offered initial insights into the functional roles of individual ferredoxins within this network. This study primarily focuses on Ferredoxin 9 (slr2059). Through sequence analysis and computational modeling, Ferredoxin 9 emerges as a unique ECP with a distinctive two-domain architecture. It consists of a C-terminal iron-sulfur binding domain and an N-terminal domain with homology to Nil-domain proteins, connected by a structurally rigid 4-amino acid linker. Notably, in contrast to canonical [2Fe-2S] ferredoxins exemplified by PetF (ssl0020), which feature highly acidic surfaces facilitating electron transfer with photosystem I reaction centers, models of Ferredoxin 9 reveal a more neutral to basic protein surface. Using a combination of electron paramagnetic resonance spectroscopy and square-wave voltammetry on heterologously produced Ferredoxin 9, this study demonstrates that the protein coordinates 2x[4Fe-4S]2+/1+ redox-active and magnetically interacting clusters, with measured redox potentials of -420 +/- 9 mV and -516 +/- 10 mV vs SHE. A more in-depth analysis of Fdx9's unique structure and protein sequence suggests that this type of Nil-2[4Fe-4S] multi-domain ferredoxin is well conserved in cyanobacteria, bearing structural similarities to proteins involved in homocysteine synthesis in methanogens.

cyanobacteria↗

Electrical Control of Structural and Physical Properties via Strong Spin-Orbit Interactions in Sr 2 IrO 4

Electrical control of structural and physical properties is a long-sought, but elusive goal of contemporary science and technology. We propose that a combination of strong spin-orbit interactions (SOI) and a canted antiferromagnetic Mott state is sufficient to attain that goal. The antiferromagnetic insulator Sr 2 IrO 4 provides a model system in which strong SOI lock canted Ir magnetic moments to IrO6 octahedra, causing them to rigidly rotate together. A novel coupling between an applied electrical current and the canting angle reduces the N´eel temperature and drives a large, nonlinear lattice expansion that closely tracks the magnetization, increases the electron mobility, and precipitates a unique resistive switching effect. Our studies open new avenues for understanding fundamental physics driven by strong SOI in condensed matter, and provide a new paradigm for functional materials and devices.

36 MATERIALS SCIENCE↗

Adaptive Individual Blade Pitch Control of an Ocean Current Turbine for Load Reduction

A Direct Adaptive Disturbance Rejection (DADR) control algorithm is evaluated using a numer-ical simulation of an Ocean Current Turbine (OCT) for its ability to minimize the cyclic loadings on the rotor blades caused by current shear. This control algorithm reduces these cyclic loadings by individually altering the pitch angles of the rotor blades as a function of rotor rotation angle. The OCT numerical model represents a system with a single 3 bladed 20 meter diameter rotor operated in the Gulf Stream off the coast of Ft. Lauderdale, Florida for mean and maximum measured current shear values of 0.004 and 0.03 (m/s)/m. The results indicate that the adaptive controller reduced the amplitude of the cyclic axial blade loads on a rigidly mounted and moored turbine by 91.18% and 92.3% in the mean current shear and by 94.12% and 81.88% in maximum current shear demonstrating the value of this controls approach.

adaptive control↗