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At least 1,585 records · Page 88

Calibration Designs for Non-Monolithic Wind Tunnel Force Balances

This research paper investigates current experimental designs and regression models for calibrating internal wind tunnel force balances of non-monolithic design. Such calibration methods are necessary for this class of balance because it has an electrical response that is dependent upon the sign of the applied forces and moments. This dependency gives rise to discontinuities in the response surfaces that are not easily modeled using traditional response surface methodologies. An analysis of current recommended calibration models is shown to lead to correlated response model terms. Alternative modeling methods are explored which feature orthogonal or near-orthogonal terms.

Wind tunnel models↗

Laser pointing determination for the geoscience laser altimeter system

The Geoscience Laser Altimeter System (GLAS) is a space-based lidar being developed to monitor changes in the mass balance of the Earth's polar ice sheets (Thomas et al. 1985). GLAS is part of NASA's Earth Observing System (Schutz 1995), and is being designed to launch into a 600 km circular polar orbit in the year 2001, for continuous operation over 3 to 5 years. The orbit's 94 degree inclination has been selected to allow good coverage and profile patterns over the ice sheets of Greenland and Antarctica. The GLAS mission uses a small dedicated spacecraft provided by Ball Aerospace, which is required to have a very stable nadir and zenith pointing platform which points to within approximately 100 urad (20 arcseconds) of Nadir. Accurate knowledge of the laser beam's pointing angle (in the far field) is critical since pointing the laser beam away from nadir biases the altimetry measurements (Gardner 1992, Bufton et al. 1991). This error is a function of the distance of the laser centroid off nadir multiplied by the orbit altitude and the tangent of the slope angle of the terrain. Most of the ice sheet surface slopes are less than 1? resulting in pointing knowledge bias of only 7.6 cm with 7.3 urad accuracy, and overall single shot height accuracy of approximately 15 cm. However, over a 3 deg surface slope pointing knowledge to approximately 7.3 urad is the largest error source (23 cm) in achieving 26 cm height accuracy. The GLAS design incorporates a stellar reference system (SRS) to relate the laser beam pointing angle to the star field to an accuracy of 7.3 urad. The stellar reference system combines an attitude determination system (ADS) operating from 4 to 10 Hz coupled to a 40 Hz laser reference system (LRS) to perform this task.

Miller, Pamela S.↗

Physiological basis for human autonomic rhythms

Oscillations of arterial pressures, heart periods, and muscle sympathetic nerve activity have been studied intensively in recent years to explore otherwise obscure human neurophysiological mechanisms. The best-studied rhythms are those occurring at breathing frequencies. Published evidence indicates that respiratory fluctuations of muscle sympathetic nerve activity and electrocardiographic R-R intervals result primarily from the action of a central 'gate' that opens during expiration and closes during inspiration. Parallel respiratory fluctuations of arterial pressures and R-R intervals are thought to be secondary to arterial baroreflex physiology: changes in systolic pressure provoke changes in the R-R interval. However, growing evidence suggests that these parallel oscillations result from the influence of respiration on sympathetic and vagal-cardiac motoneurones rather than from baroreflex physiology. There is a rapidly growing literature on the use of mathematical models of low- and high-frequency (respiratory) R-R interval fluctuations in characterizing instantaneous 'sympathovagal balance'. The case for this approach is based primarily on measurements made with patients in upright tilt. However, the strong linear relation between such measures as the ratio of low- to high-frequency R-R interval oscillations and the angle of the tilt reflects exclusively the reductions of the vagal (high-frequency) component. As the sympathetic component does not change in tilt, the low- to high-frequency R-R interval ratio provides no proof that sympathetic activity increases. Moreover, the validity of extrapolating from measurements performed during upright tilt to measurements during supine rest has not been established. Nonetheless, it is clear that measures of heart rate variability provide important prognostic information in patients with cardiovascular diseases. It is not known whether reduced heart rate variability is merely a marker for the severity of disease or a measurement that identifies functional reflex abnormalities contributing to terminal dysrhythmias.

Review, Tutorial↗

A "Bony" Proposition: Pathways Mediating Responses to Simulated Weightlessness and Radiation

There is evidence that weightlessness and radiation, two elements of the spaceflight environment, can lead to detrimental changes in human musculoskeletal tissue, including bone loss and muscle atrophy. This bone loss is thought to be brought about by the increased activity of bone-resorbing osteoclasts and functional changes in bone-forming osteoblasts, cells that give rise to mature osteocytes. My current area of research focuses on understanding the mechanistic basis for the responses of bone to the spaceflight environment using earth-based animal and cellular models. The overarching goal is to identify molecular targets to prevent bone loss in space exploration and earth-based scenarios of radiotherapy, accidental radiation exposure and reduced mobility. In this talk, I will highlight two signaling pathways that potentially play a role in the response of bone to spaceflight-like conditions. Firstly, I will discuss the role of insulin-like growth factor 1 (IGF1) signaling as it pertains to the recovery of bone from simulated weightlessness (rodent hindlimb unloading model). Secondly, I will share recent findings from our study that aims to understand the emerging role of autophagy in maintaining the balance between bone formation and resorption (bone homeostasis) as well as normal skeletal structure.

autophagy↗

Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution

Understanding the effects of polymer brush architecture on particle interactions in solution is requisite to enable the development of functional materials based on self-assembled polymer-grafted nanoparticles (GNPs). Static and dynamic light scattering of polystyrene-grafted silica particle solutions in toluene reveals that the pair interaction potential, inferred from the second virial coefficient, A 2 , is strongly affected by the grafting density, σ, and degree of polymerization, N, of tethered chains. In the limit of intermediate σ (~0.3 to 0.6 nm -2 ) and high N, A 2 is positive and increases with N. This confirms the good solvent conditions and can be qualitatively rationalized on the basis of a pair interaction potential derived for grafted (brush) particles. In contrast, for high σ > 0.6 nm -2 and low N, A 2 displays an unexpected reversal to negative values, thus indicating poor solvent conditions. These findings are rationalized by means of a simple analysis based on a coarse-grained brush potential, which balances the attractive core-core interactions and the excluded volume interactions imparted by the polymer grafts. The results suggest that the steric crowding of polymer ligands in dense GNP systems may fundamentally alter the interactions between brush particles in solution and highlight the crucial role of architecture (internal microstructure) on the behavior of hybrid materials. The effect of grafting density also illustrates the opportunity to tailor the physical properties of hybrid materials by altering geometry (or architecture) rather than a variation of the chemical composition.

36 MATERIALS SCIENCE↗

Characterization of Days Based On Analysis of National Airspace System Performance Metrics

Days of operations in the National Airspace System can be described in term of traffic demand, runway conditions, equipment outages, and surface and enroute weather conditions. These causes manifest themselves in terms of departure delays, arrival delays, enroute delays and traffic flow management delays, Traffic flow management initiatives such as, ground stops, ground delay programs, miles-in-trail restrictions, rerouting and airborne holding are imposed to balance the air traffic demand with respect to the available capacity, In order to maintain operational efficiency of the National Airspace System, the Federal Aviation Administration (FAA) maintains delay sad other statistics in the Air Traffic Operations Network (OPSNET) and the Aviation System Performance Metrics (ASPM) databases. OPSNET data includes reportable delays of fifteen minutes ox more experienced by Instrument Flight Rule (IFR) flights. Numbers of aircraft affected by departure delays, enroute delays, arrival delays and traffic flow delays are recorded in the OPSNET data. ASPM data consist of number of actual departures, number of canceled departures, percentage of on time departures, percentage of on time gate arrivals, taxi-out delays. taxi-in delays, gate delays, arrival delays and block delays. Surface conditions at the major U.S. airports are classified in terms of Instrument Meteorological Condition (IMC) and Visual Meteorological Condition (VMC) as a function of the time of the day in the ASPM data. The main objective of this paper is to use OPSNET and ASPM data to classify the days in the datasets into few distinct groups, where each group is separated from the other groups in terms of a distance metric. The motivations for classifying the days are two-fold, 1) to enable selection of days of traffic with particular operational characteristics for concept evaluation using system-wide simulation systems such as the National Aeronautics and Space Administration's Airspace Concepts Evaluation Tool (ACES) and 2) to enable evaluation of a given day with respect to the characteristics of the classified groups. The first part of the paper is devoted to the analysis of major trends seen in the OPSNET and ASPM data. The second part of the paper is devoted to describing features or measures derived from the OPSNET and ASPM data that are suitable for characterizing days, and the classification algorithm used for grouping the days. Finally, the method for evaluating the characteristics of a given day with respect to the properties of the groups is described.

Chatterji, Gano B.↗

Unconventional ferroelectricity in moiré heterostructures

Although all matter is composed of component particles, these particles can arrange themselves in various ways, giving rise to emergent phenomena that can be surprisingly rich and often cannot be understood by studying only the individual constituents. Discovering and understanding novel forms of emergence in quantum materials, especially in those where multiple degrees of freedom or energy scales are delicately balanced, is of great fundamental interest to condensed matter research. In this work, we report on the surprising observation of emergent ferroelectricity in graphene-based moiré heterostructures. Ferroelectric materials exhibit an electrically-switchable electric dipole, which is usually formed by spatial separation between the averaged centers of positive and negative charge within the unit cell. Based on this, it is difficult to imagine graphene, a material composed only of carbon atoms, exhibiting ferroelectricity. However, in this work, we indeed realize switchable ferroelectricity in Bernal-stacked bilayer graphene sandwiched between two hexagonal boron nitride (BN) layers. By introducing a moiré superlattice potential (via aligning bilayer graphene with the top and/or bottom BN crystals), we observe prominent and robust hysteretic behavior of the graphene resistance with an externally applied out-of-plane displacement field. Our systematic transport measurements reveal rich and striking response as a function of displacement field and electron filling, not previously observed in any 2D systems, and beyond the framework of conventional ferroelectrics. We further directly probe the ferroelectric polarization through a nonlocal monolayer graphene sensor. Our results suggest an unconventional, odd parity electronic ordering in the bilayer graphene/BN moiré system. This emergent moiré ferroelectricity may pave the way for ultrafast, programmable, and atomically thin carbon-based memory devices.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Scanning Mobility Particle Sizer (SMPS)-Aerodynamic Particle Sizer (APS) Merged Size Distribution (mergedsmpsaps) Value-Added Product Report

Aerosol particles influence the Earth’s radiation balance directly by absorbing and scattering light and indirectly by influencing cloud formation, properties, and lifetimes. Measurements of aerosol particle optical properties, mass loading, size distributions, microphysical properties, cloud formation properties, and chemical composition are important for understanding the aerosol life cycle and for validating earth system models that predict these quantities. The Atmospheric Radiation Measurement (ARM) user facility’s Aerosol Observing System (AOS) is a highly instrumented platform designed to house instruments that measure many of these aerosol properties in situ. Currently, ARM operates at least four different instruments that measure a portion of the ambient aerosol size distribution. Most users are interested in the entire size distribution or a portion of the size distribution that extends across the measurement range of multiple instruments. However, merging these distributions is not trivial as the instruments employ different measurement principals and, in most cases, report data as a function of different representations of the aerosol diameter.

54 ENVIRONMENTAL SCIENCES↗

Sensory-Motor Adaptation to Space Flight: Human Balance Control and Artificial Gravity

Gravity, which is sensed directly by the otolith organs and indirectly by proprioceptors and exteroceptors, provides the CNS a fundamental reference for estimating spatial orientation and coordinating movements in the terrestrial environment. The sustained absence of gravity during orbital space flight creates a unique environment that cannot be reproduced on Earth. Loss of this fundamental CNS reference upon insertion into orbit triggers neuro-adaptive processes that optimize performance for the microgravity environment, while its reintroduction upon return to Earth triggers neuro-adaptive processes that return performance to terrestrial norms. Five pioneering symposia on The Role of the Vestibular Organs in the Exploration of Space were convened between 1965 and 1970. These innovative meetings brought together the top physicians, physiologists, and engineers in the vestibular field to discuss and debate the challenges associated with human vestibular system adaptation to the then novel environment of space flight. These highly successful symposia addressed the perplexing problem of how to understand and ameliorate the adverse physiological effects on humans resulting from the reduction of gravitational stimulation of the vestibular receptors in space. The series resumed in 2002 with the Sixth Symposium, which focused on the microgravity environment as an essential tool for the study of fundamental vestibular functions. The three day meeting included presentations on historical perspectives, vestibular neurobiology, neurophysiology, neuroanatomy, neurotransmitter systems, theoretical considerations, spatial orientation, psychophysics, motor integration, adaptation, autonomic function, space motion sickness, clinical issues, countermeasures, and rehabilitation. Scientists and clinicians entered into lively exchanges on how to design and perform mutually productive research and countermeasure development projects in the future. The problems posed by long duration missions dominated these discussions and were driven by the paucity of data available. These issues along with more specific recommendations arising from the above discussions will be addressed an upcoming issue of the Journal of Vestibular Research.

Paloski, William H.↗

An Alternative Inter-Satellite Calibration of the UMD HIRS OLR Retrievals

Outgoing Longwave Radiation (OLR) at the top-of-atmosphere (TOA) is a fundamental component of Earth's energy balance and represents the heat energy in the thermal bands rejected to space by the planet. Determination of OLR from satellites has a long and storied history, but the observational record remains largely fragmented with gaps in satellite measurements over the past three decades. Perhaps the most semi-continuous set of retrievals comes from the University of Maryland (UMD) algorithm that uses four HIRS (High Resolution Infrared Sounder) channels on the NOAA polar orbiting satellites to estimate OLR. This data set shows great promise in helping to bridge the discontinuous ERBS (Earth Radiation Budget Satellite) and CERES (Clouds and the Earth s Radiant Energy System) measurements. However, significant satellite inter-calibration biases persist with the present UMD data, principally outside the tropics. Difficulties relate to the combination of drift of the satellite equator crossing time through the diurnal cycle and changes in HIRS channel response function design. Here we show how an ad hoc recalibration of the UMD retrievals among the different satellites removes much of the remaining uncertainty due to diurnal drift of the satellite orbit. The adjusted HIRS data (using no other external information) show much better agreement with OLR from the European Center Interim Reanalysis (EC-Int), longer-term signals in the Global Energy and Water Cycle Experiment / Surface Radiation Budget (GEWEX/SRB) retrievals, and also agree well with ERBS and CERES OLR measurements. These results augur well for narrowing the uncertainties in multi-decadal estimates of this important climate variable.

Robertson, Franklin R.↗

Anthropogenic Perturbations to the Atmospheric Molybdenum Cycle

Abstract Molybdenum (Mo) is a key cofactor in enzymes used for nitrogen (N) fixation and nitrate reduction, and the low availability of Mo can constrain N inputs, affecting ecosystem productivity. Natural atmospheric Mo aerosolization and deposition from sources such as desert dust, sea‐salt spray, and volcanoes can affect ecosystem function across long timescales, but anthropogenic activities such as combustion, motor vehicles, and agricultural dust have accelerated the natural Mo cycle. Here we combined a synthesis of global atmospheric concentration observations and modeling to identify and estimate anthropogenic sources of atmospheric Mo. To project the impact of atmospheric Mo on terrestrial ecosystems, we synthesized soil Mo data and estimated the global distribution of soil Mo using two approaches to calculate turnover times. We estimated global emissions of atmospheric Mo in aerosols (<10 μm in diameter) to be 23 Gg Mo yr −1 , with 40%–75% from anthropogenic sources. We approximated that for the top meter of soil, Mo turnover times range between 1,000 and 1,000,000 years. In some industrialized regions, anthropogenic inputs have enhanced Mo deposition 100‐fold, lowering the soil Mo turnover time considerably. Our synthesis of global observational data, modeling, and a mass balance comparison with riverine Mo exports suggest that anthropogenic activity has greatly accelerated the Mo cycle, with potential to influence N‐limited ecosystems.

Wong, Michelle Y.↗

A Computational Framework to design 3D stiffness gradient acoustic metamaterials for impedance matching

Acoustic waves play a crucial role in various applications, including medical imaging, non-destructive testing, and sonar systems. One of the significant challenges in these applications is impedance matching, which is essential for minimizing reflections and maximizing the transfer of acoustic energy between different media. Acoustic metamaterials offer a promising solution to this challenge. In addition to impedance control, gradient stiffness can enhance structural efficiency and enable spatial control of wave propagation, making it a valuable feature in acoustic metamaterial design. In this pa- per, we present our developed computational method to design 3D stiffness gradient acoustic metamaterials for impedance matching. The key steps in our approach include generating initial designs using a periodic covariance function to provide unit cells that are both periodic on the boundaries and randomly formed inside the unit cell. Furthermore, we integrated manufacturing constraints into the design process, ensuring that the structures are interconnected for fabrication. We propose two computational optimization algorithms: GenUnit, based on a non-dominated sorting genetic algorithm (NSGA-II), and MLMatch, which leverages differentiable machine learning. The two approaches are not separate contributions but complementary com- ponents of a unified framework. GenUnit requires no training data and directly interfaces with physics-based simulations, making it highly accurate but slower for large-scale exploration. In contrast, MLMatch is data-hungry during training but, once trained, enables near-instantaneous inference and broad design-space coverage. Together, they form a hybrid strategy: ML- Match rapidly explores the global design space, and GenUnit provides local refinement with high-fidelity accuracy. This balance between training cost, inference time, and precision is the motivation for including both methods in the same study. We applied this dual-algorithm framework to generate two metallic-based metamaterial designs that match the acoustic impedance of water while exhibiting a controlled gradient in stiffness (from stiff to soft). The stiffness gradient is particularly advantageous in applications where one side of the structure must interface with soft or sensitive surfaces, such as human tissue or delicate components. Here, this work paves the way for improved materials in various acoustic applications, particularly in ultrasound devices, by providing better impedance.

Metamaterial↗

Atomic Orbital Energy Matching vs Overlap in Actinide-Ligand Dative Bonding

Prebonding conditions and dative bond formation in actinide(IV)hexachloride complexes with U, Np, and Pu are studied by density functional theory (DFT) calculations, focusing on the interplay of atomic orbital (AO) overlap and AO energy matching in the formation of molecular orbitals (MOs) and the subsequent identification of dative bonds. The extent of donation is tracked via population analysis, MO localization, and bond-order criteria. DFT Fock matrices are used to setup models in which varying numbers of valence AOs interact to form dative bonds. The results confirm, among other effects, a contribution to metal−ligand covalency from the actinide (An) 6p shell. Better matching of An(5f) and Cl(3p) energies occurs as the An(5f) level stabilizes with increasing An effective nuclear charge. A near-degeneracy occurs in the case of the α-spin orbitals of the Pu system, but it is inconsequential. Altogether, better AO energy matching for An(5f) and Cl(3p) along the series U, Np, Pu is counter-balanced by decreasing AO overlap and decreasing availability of 5f acceptor orbitals, leading to similar bond orders and extents of donation in the three systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DECOVALEX-2023: Task E Final Report

This is the Task E final report for DECOVALEX-2023. Task E is focused on understanding thermal, two-phase hydrological, and mechanical (TH2M) processes, especially related to predicting brine migration in the excavation damaged zone around a heated excavation in salt. Salt is attractive as a disposal medium for radioactive waste because it is self-healing and is essentially impermeable and essentially non-porous in the far field (away from excavations). Investigation of the short-term (days to years) near-field (centimeters to tens of meters) behavior of salt is important for radioactive waste disposal because this early period strongly controls the amount of brine in a salt repository. Brine leads to corrosion of waste forms and waste packages, and possible dissolution of radionuclides with brine transport being a potential transport vector to the accessible environment. The main test case used in Task E is the ongoing Brine Availability Test in Salt (BATS) heater test located underground at the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico, USA. The Task was divided into a series of Steps. Step 0 was an introduction to processes in salt, that included matching historical unheated brine inflow data from boreholes at WIPP and matching temperature observations during BATS heater test 1a. Step 1 included validation of models against a thermo-poroelastic analytical solution relevant to heated boreholes in salt, and two-phase flow around an excavation in salt. Step 2 required all the individual components covered in steps 0 and 1 to come together to match observed brine inflow behavior during the BATS 1a heater test. There were a range of approaches from the teams, from mechanistic to prescriptive. Given the uncertainties in the problem, some teams used one- or two-dimensional models of the processes, while other teams included more geometrical complexity in three-dimensional models. The key learning points from Task E have been: • Heat conduction through salt typically requires non-linear thermal conductivity (as a function of temperature), but most models do a good job matching observations, given appropriate adjustments to the applied power and some thermocouple locations. • Thermal pressurization requires coupled thermal-hydrological-mechanical (THM) responses that consider the thermal expansion of the fluid and solid phases. • Initialization of two-phase flow models around a borehole or excavation in salt are more realistically represented as “wetting up”, rather than “drying down” (i.e., the initial state after excavation is mostly dry, rather than mostly wet). • The BATS 1a heater test includes a significant release of brine after the end of heating, which requires a large increase in permeability to recreate. Task E has been a great learning experience for all the teams involved, and feedback from the modeling teams has led to changes in the design of follow-on BATS experiments, which are now ongoing underground at WIPP. There was a balance throughout the task between freedom to model phenomena how each team saw fit, and prescriptiveness in problem design to bring the modeling teams closer together to allow attribution of smaller differences between models to different modeling choices. The modeling approaches seem to go through two phases: an early phase of discovery or testing, and a later phase of refinement and improvement. In future modeling efforts, different field data could be used (e.g., BATS 2) and more time should be included in the processes for teams to make multiple model refinement or even significant changes to their conceptual model or setup, based on lessons learned from the modeling exercise.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Diagnostic calculations of the circulation in the Martian atmosphere

The circulation of the Martian atmosphere during late southern summer is derived from atmospheric temperature and dust distributions retrieved from a subset of the Mariner 9 infrared interferometer spectrometer (IRIS) thermal emission spectra (L(sub s) = 343-348 deg). Zonal-mean zonal winds are calculated by assuming gradient wind balance and zero surface zonal wind. Both hemispheres have intense midlatitude westerly jets with velocities of 80-90 m/s near 50 km; in the southern tropics the winds are easterly with velocities of 40 m/s near 50 km. The net effect of the zonal mean meridional circulation and large-scale waves can be approximated by the diabatic circulation, which is defined from the atmospheric thermal structure and net radiative heating rates. The radiative transfer model described by Crisp (1990) and Santee (1993) is used to compute solar heating and thermal cooling rates from diurnal averages of the retrieved IRIS temperature and dust distributions. At pressures below 4 mbar, there are large net radiative heating rates (up to 5 K/d) in the equatorial region and large net radiative cooling rates (up to 12 K/d) in the polar regions. These net radiative heating rates are used in a diagnostic stream function model which solves for the meridional and vertical components of the diabatic circulation simultaneously. We find a two-cell circulation, with rising motion over the equator, poleward flow in both hemispheres, sinking motion over both polar regions, and return flow in the lowest atmospheric levels. The maximum poleward velocity is 3 m/s in the tropics at approx. 55 km altitude, and the maximum vertical velocity is 2.5 cm/s downward over the north pole at approx. 60 km altitude. If these large transport rates are sustained for an entire season, the Martian atmosphere above the 1-mbar level is overturned in about 38 days. This diabatic circulation is qualitatively similar to the terrestrial diabatic circulation at the comparable season, but is more vigorous.

Santee, Michelle L.↗

The Effect of Age in the Alteration in Fluid Balance of Rats in Response to Centrifugation

With an increase in gravity load induced by centrifugation or upon return to Earth following spaceflight, there is a period of adjustment in fluid balance in rats. With centrifugation there is a reduced fluid intake with maintenance of the rate of urine excretion. Following spaceflight there is an increase in urine output and maintenance of fluid intake. The initial period of acclimation to hypergravity is associated with a net loss of fluids. In the present study in response to centrifugation at 2.0 G this period of acclimation is present in mature rats for a longer period of time, about 24 hours. Following this initial response a period of over compensation has previously been reported. In the present study this was not observed. The net effect of these alterations in water intake and output in response to centrifugation for 14 days was slight increase in the percent total body water, with effective compensation seen in both young and mature rats. Older rats have been shown to have a reduced relative thirst and compensatory renal function in response to hypohydration, hyperosmolality and pharmacological stimuli. Responsiveness to these stimuli are delayed and/or attenuated in older animals. Similar findings were noted in the present study in the initial response to centrifugation. The older animal had a delayed return of fluid intake to control levels. The delay of one day did not appear to effect long-term fluid homeostasis, as there was difference in the response of percent total body water at the end of 14 days of centrifugation with both age groups having a slight but significant increase. This increase has been attributed to the increase in lean body mass induced by centrifugation.

Fuller, Charles A.↗

Molecular Level Understanding of Polyethylene Terephthalate (PET) Depolymerization in Base/Alcohol Hybrid Systems

Polyethylene terephthalate (PET) depolymerization in base/alcohol hybrid systems represents a promising low-energy approach for chemically recycling PET waste into valuable monomers. This study investigates the mechanistic pathways of PET depolymerization in NaOH/alcohol solutions, emphasizing the competing roles of hydroxide and alkoxide species. Utilizing a combination of experimental techniques, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations, we explore how factors such as base concentration, alcohol chain length, and pKa values of alcohols influence PET depolymerization efficiency and pathways. Our findings indicate that alkoxide ions (RO⁻) exhibit notably higher reactivity than hydroxide ions (HO⁻), favoring an alcoholysis pathway in the base/alcohol hybrid system. Experimental results across a series of C1 to C5 alcohols show that longer-chain alcohols, particularly 1-butanol, achieve higher PET conversion, although this does not align solely with simple nucleophilicity trends of alkoxides. While DFT calculations reveal comparable activation energies for various alkoxides in PET depolymerization, MD simulations underscore the significant role of alcohol chain length, with longer-chain alcohols forming more stable or frequent interactions with PET. Additionally, the alkoxide concentration, influenced by the alcohol’s pK a , directly impacts PET conversion. These suggest that PET depolymerization is governed by a balance between alkoxide concentration and alkoxide-PET interactions, rather than activation energies or nucleophilicity alone. From a practical perspective, incorporating long-chain alcohols as cosolvents may enhance process efficiency but increases raw material costs by approximately 30%. However, long-chain alcohols present a safer and more sustainable alternative to hazardous cosolvents such as dichloromethane. This work offers a molecular-level understanding of PET depolymerization in base/alcohol systems and provides insights into optimizing these systems for more efficient and sustainable PET recycling processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water-enhanced bifunctional metal-acid catalyst for C=C bond hydrogenation

Water-assisted proton shuttling can promote hydrogenation of polar functional groups, and it is generally believed that such an effect can be hardly applied to hydrogenation of C═C bonds due to the latter's weak interaction with water. Here, we report density functional theory calculations and metadynamics simulations, through which we show a dynamic bifunctional metal–acid site that can be transformed, when interacting with water, into an active configuration for unexpected water-enhanced proton shuttling to C═C bonds. In particular, we investigated B(OH)3 anchored to a Ni catalyst for hydrogenation of cyclohexene in an organic solvent, which showed in experiments an increased rate by 100 times when adding a small amount of water. Metadynamics simulations suggest that a B(OH)3–H2O cluster can form on Ni(111), which promotes the proton transfer in the first hydrogenation step, while the second hydrogenation is still driven by metal-mediated direct H-transfer. The recovery process of B(OH)3–H2O also involves a proton shuttling step. We find that the boric species on the surface serves as an electron reservoir and carries the negative charge to balance the positive charge in the proton transfer steps. This work thus provides fundamental insights into this dynamic transformation process of the metal–acid interface, which can in principle be applied to many other bifunctional systems for hydrogenating non-polar unsaturated groups by engineering the interfacial charge separation.

Sun, Shoutian↗