Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “snapshot”

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

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 271 records · Page 15

Modeling Mg II During Solar Flares. I. Partial Frequency Redistribution, Opacity, and Coronal Irradiation

The Interface Region Imaging Spectrograph has routinely observed the flaring Mg II near-ultraviolet (NUV) spectrum, offering excellent diagnostic potential and a window into the location of energy deposition. A number of studies have forward-modeled both the general properties of these lines and specific flare observations. Generally these have forward-modeled radiation via post-processing of snapshots from hydrodynamic flare simulations through radiation transfer codes. There has, however, not been a study of how the physics included in these radiation transport codes affects the solution. A baseline setup for forward-modeling Mg II in flares is presented and contrasted with approaches that add or remove complexity. It is shown for Mg II that (1) partial frequency distribution (PRD) is still required during flare simulations despite the increased densities; (2) using full angle-dependent PRD affects the solution but takes significantly longer to process a snapshot; (3) including Mg I in non-LTE (NLTE) results in negligible differences to the Mg II lines but does affect the NUV quasi-continuum; (4) only hydrogen and Mg II need to be included in NLTE; (5) ideally the nonequilibrium hydrogen populations, with nonthermal collisional rates, should be used rather than the statistical equilibrium populations; (6) an atom consisting of only the ground state, h and k upper levels, and continuum level is insufficient to model the resonance lines; and (7) irradiation from a hot, dense flaring transition region can affect the formation of Mg II. We discuss modifications to the RH code allowing straightforward inclusion of the transition region and coronal irradiation in flares.

Kerr, Graham S.↗

Optical Flow for Intermediate Frame Interpolation of Multispectral Geostationary Satellite Data

Applications in areas such as weather tracking and modeling, ecosystem monitoring, wildfire detection, and land-cover change are heavily dependent on spatial and temporal resolutions of satellite observations. However, there are typically trade-offs between spatial and temporal resolutions in dataset selection. For instance, geostationary weather tracking satellites are designed to take snapshots many times throughout the day but sensor hardware limits data collection. In this work we tackle this limitation, developing a method for temporal upsampling of multi-spectral satellite imagery using optical flow video interpolation deep convolutional neural networks. The presented model, extends Super SloMo (SSM) from single optical flow estimates to multichannel where flows are computed per band. We apply this technique on 8 multi-spectral bands of NOAA/NASA's GOES-16 mesoscale dataset to temporally enhance full disk hemispheric snapshots from 15 minutes to 1 minute. Through extensive experimentation, we show SSM vastly outperforms the linear interpolation baseline and that multichannel optical flows improves performance on GOES-16. A visual analysis of optical flow vectors clearly identifies hurricanes and large-scale atmospheric dynamics. Furthermore, we discuss challenges and open questions related to optical flow and temporal interpolation of multispectral geostationary satellite imagery.

Optical Flow↗

Combining MODIS LAI with ICESat-Based Canopy Heights Improves Spaceborne Estimates of Vegetation Roughness Length for Momentum

Most land-surface models require parameterization of vertical wind profiles within the atmospheric boundary layer. For vegetated surfaces, it is common to assume a logarithmic profile in the surface layer, which includes estimates of vegetation roughness length for momentum (z0) and zero-plane displacement height (d0). This study finds that remotely-sensed forest canopy heights improve estimates of aerodynamic roughness length for momentum using a previously-developed representation of the roughness sublayer (Raupach 1992; Jasinski et al. 2005). Resulting roughness products consist of two datasets: 1) 14 years of 8-day snapshots of the global land surface at a nominal spatial resolution of 500-meters for users who wish to retain full temporal resolution and interannual variability; and 2) multiyear averages of the 8-day snapshots, here referred to as "climatologies" of roughness, which retain underlying seasonality. Both products are suitable for use in data assimilation and reanalyses such as the National Climate Assessment Land Data Assimilation System (NCA-LDAS), for which these products were initially developed.

Borak, Jordan S.↗

Monitoring Airspace Complexity and Determining Contributing Factors

The national airspace has evolved over many years to accommodate increased traffic demand [1] while simultaneously maintaining one of the safest forms of transportation [2], [3]. One of the reasons for this success is the ability of the system and the operators to adapt and accommodate to situations that routinely disrupt optimal operations. These situations may include: adverse weather, delays, early arrivals, equipment outages, and other factors that are outside the operators ability to control. These factors can lead to states where automation is unable to properly handle these issues and therefore air traffic controllers and pilots have to intervene, ultimately increasing communication between operators resulting in higher workload. As controller workload increases to handle sub-optimal operating conditions this can be viewed as an increase in complexity. The reasoning for this is because humans are now required to make tactical decisions in response to external factors, resulting in a departure from the strategic plan where operations would be more efficiently managed. Human operators control airspace complexity under rigid regulations that are constantly changing. The airspace is divided into sectors and the number of aircraft assigned to each controller is limited for safe handling. There has been past work that devised airspace complexity metrics in commercial aviation and related these metrics to controller workload (e.g., [4],[5]). The upper bounds on the system load are pre-determined. Such bounds on complexity make for a safe system, but the system cannot scale and adapt to autonomous, dense, and heterogeneous traffic, including the many types of Unmanned Aerial Vehicles (UAVs) envisioned to be added to the operations. We hypothesize that, as traffic density and heterogeneity grow, and other key metrics change, there will be phase transitions at which the way traffic should be managed changes significantly [6]. We offer a method for in-time detection of contributing factors that lead to phase transitions, characterized by increased complexity. To the best of our knowledge, there is no tool similar to our proposed effort that identifies such contributing factors or precursor patterns. To define the scope we are proposing to measure complexity from the viewpoint of the Terminal Radar Approach Control Facilities (TRACON) controller’s perspective. In particular we are analyzing arrivals into KSFO. With safety as the top concern for airspace operators, it is important to recognize that as density and heterogeneity grow, the focus of the system will change. Times of the day when the airspace has low density and heterogeneity, the flights will follow more efficient paths where the aircraft move on established routes that are more or less directly to the destination. However, when density and heterogeneity increases, the system will begin changing focus to avoiding conflicts and collisions and route the flights in a more flexible way. Higher flexibility requires more communication and coordination between controllers and pilots which the current automation is unable to handle. This paper proposes a novel approach that monitors airspace complexity at multiple scales, uses a Machine Learning-based tool that predicts when operations will transition to a regime of greater complexity, and identifies actions that can reduce the complexity while still maintaining efficient and safe operations. We demonstrate our proposed approach using data from multiple complementary sources. This includes, but is not limited to: historical aircraft surveillance data from NASA’s Sherlock Data Warehouse [7], METAR weather data, and airport configuration data from Aviation System Performance Metrics (ASPM). The surveillance data flight paths are sampled at a variable sample rate — increasing as the aircraft approaches the airport. This is due to how Sherlock manages flight track stitching between different radar facilities which have different sampling rates. The weather and performance data are logged at defined intervals throughout the day at a courser refresh rate. In addition to the logged data and metrics, we leverage pre-defined Standard Terminal Arrival Routes (STARs) procedures to characterize the path of each flight. Each flight files for one of these routes in the flight plan well before entering the terminal airspace, and approximately follows the route until it leaves the STAR, typically on the final fix of a runway transition. However, most flights do not always fly the full STAR procedure to completion [8], but the majority do adhere to the fixes within the common route of the procedure. Our approach leverages fixes in the common route of each of the STARs to build a reference path to the airport. This allows us to characterize the flight paths in what we are defining as the “maneuvering area” (the airspace between the STAR and before the flight is lined up on the runway’s final approach) to determine how off nominal the flights are to calculate its complexity score. Determining airspace complexity is a concept that does not have a concrete answer. In designing this metric, we consider what increases the workload for the air traffic controllers. Consequently more specialized vectoring maneuvers results in higher workload. Accordingly, we start with a theory: each flight has a direct path it takes from the STAR’s common route to the final approach’s outer marker fix for the flight’s landing runway. It is important to note that the direct path is only used as a reference. If the majority of the flights have a large consistent offset as compared to other routes it does not necessarily mean that those flights have higher complexity. We are merely building a distribution based on this direct path for that particular STAR and runway pair to determine the normal mode of operations for that route. Flights that are in the upper tail of these distributions will result in higher complexity scores and flights that fly in the median will represent the normal mode of operations and therefore will have lower complexity scores. Since flights following each STAR route take different paths to the airport, we have a different distribution for each STAR route and therefore can model these distributions to compute a complexity score from their respective normalized distributions. To evaluate the effectiveness of our proposed airspace complexity metric we will compare against an established approach based on trajectory clustering [9]. This unsupervised learning technique consists of the following steps: (1) identify the general maneuvering areas (waypoints) by performing $\kappa$-means or DBSCAN clustering on locations where aircraft frequently turn based on the surveillance radar track data, (2) map flight trajectories onto sequences of waypoints, and (3) cluster the sequences based on their common subsequences. From a high-level perspective, this baseline model learns nominal operations in the airspace through the sequence of waypoints that are representative of where aircraft change direction and defines deviations from the nominal operations as “complex.” Therefore, more deviations from the nominal operations correspond to higher complexity values. For our validation, we re-implemented this technique and tune model hyper-parameters to correctly detect waypoints for the arrival traffic into the San Francisco bay area. We will compute the complexity measure over a one-year period using our proposed technique as well as the baseline. Our validation will be based on each technique’s ability to detect a set of undesirable outcomes (e.g., go-arounds, holding patterns, average time in the airspace, etc.). Since our current complexity metric is derived from the offset from the direct reference path, it’s important to understand what causes these offsets. In many of the flights with high offset distance, flights performing holding patterns and S turns can be observed. These maneuvering tactics are utilized to add distance between the aircraft and the destination runway to prevent multiple flights from having conflicting arrival times. In order to predict a rise in complexity (or the precursor to complexity), it’s necessary to be able to identify these potential conflicts (which in turn, result in higher offsets). To do this, we define a “representative flight” for each STAR route and runway pair. This flight is approximately the path the flight would take if there was a clear path with no other flights in the airspace — including the time remaining to the airport. We first identify the flights for a given STAR runway pair using the offset to the reference path distributions that fall between the 44-55 percentiles. This yields the flights that conform to the most normal mode of operation. Each of these flights is partitioned based on the percent complete from the entry point into the maneuvering areas from 0\% – 100\% complete. Then for each percent “bin”, we take the median value of the flight’s latitude/longitude coordinates, airspeed, and (non causal) time remaining to the airport to construct a lookup table for each percent complete bin on a given route. As a flight enters the maneuvering area, we can find the estimated arrival time of a flight to the airport by finding the closest point to the representative path’s percent complete bin (relative to the flight’s current position at any snapshot in the airspace) and therefore retrieve the corresponding remaining time left on the “representative path”. We assume that the flight will follow the representative path to completion when deriving these estimates. We can then compare these estimated arrival times against other flights for the same snapshot in time to identify potential conflicts. If more flights are estimated to arrive within a tolerance window than there are runways available, then we have a potential conflict. We can use this derived measure along with other factors expected to add disruption to the operation such as weather and runway configuration changes as an input to machine learning tools to detect precursors that increases in our complexity measure. This novel method will assist in uncovering insights into the contributing factors that lead to increased complexity that may allow for in-time responses to avoid reaching a high complexity state in the airspace.

complexity↗

Construction of a Fluid Flowfield from Discrete Point Data using Machine Learning

Many verification and validation procedures in aerospace engineering involve the comparison of computational fluid dynamics (CFD) data to experimental results from sources like wind tunnel tests. However, an incongruity exists between the data available from these sources: flow visualization is available by default in computational data, whereas in most experimental setups the available data is far more discrete and far more limited: integrated forces and moments, discrete pressure and temperature probes, etc. When differences exist between quantities of interest like lift and drag coefficients, the lack of full-field flow data from the experiments complicates most attempts to reconcile why the different data sources disagree. To this end, a shallow neural network, constrained by certain fluid flow properties, was trained to approximate flow field snapshots given only discrete data like that available in a wind tunnel test. The constructed snapshots, even for complex incompressible fluid flows, were found to agree at the large scales with the true flow fields. With this tool, researchers can more readily and easily understand why quantities of interest differ between their experimental and computational datasets. This in turn improves the resulting data's uncertainty measures.

Yury Lebedev↗

Expanding the Time Dimension of Hyperspectral Infrared Sounding Observations: Designing the NUCAPS-Forecast System

Low Earth orbit (LEO) hyper-spectral infrared (IR) sounders have significant yet untapped potential for characterizing thermodynamic environments of convective initiation and ongoing convection. While LEO soundings are of enormous value to weather forecasters, they cannot provide the temporal resolution needed to resolve the rapidly evolving thermodynamics of the convective environment. A novel methodology was developed to extend snapshots of LEO soundings forward in time up to six hours into the future and has been made available within the NOAA National Weather Service Advanced Weather Interactive Processing System (AWIPS) for testing in a quasi-operational setting. This methodology is based on parcel forward-trajectory calculations from the satellite observing time to recreate future soundings of temperature and moisture at regularly gridded intervals in space and time. The soundings are based on NOAA-Unique Combined Atmospheric Processing System (NUCAPS) retrievals from the Suomi NPP and NOAA-20 satellite platforms to allow for rapid near-real time product processing. Science code was transitioned to operational production in 2019 and the product, NUCAPS-Forecast, was tested at the NOAA Hazardous Weather Testbed Spring Experiment in 2019 and 2021. Forecaster feedback has led to improving the product and processing system to address product limitations and improve its applicability for pre-convective forecasting. This presentation highlights the design of the NUCAPS-Forecast system. Solutions were tested and implemented to remove excess moisture and conjoin forward-trajected parcels into vertical profiles for calculating grids of stability indices. Additionally, use cases that explore the tendencies of derived convective available potential energy (CAPE) and convective inhibition (CIN) were investigated. When evaluated against gridded, hourly accumulated rainfall obtained from the Multi-Radar Multi-Sensor (MRMS) observational data set areas with elevated CAPE (reduced CIN) are shown to be associated with areas of precipitation and increase confidence the LEO soundings advected forward in time physically represent atmospheric processes. These results suggest that adiabatic parcel advection of LEO satellite sounding snapshots forward in time exhibits skill in discriminating locations and times that are more likely to lead to convective initiation. Leveraging trajectory modeling to increase the spatial and temporal resolution of LEO IR sounding observations today demonstrates the value of these observations from the future constellation of JPSS satellites and GeoXO mission.

weather↗

Construction of a Fluid Flowfield from Discrete Point Data using Machine Learning

Many verification and validation procedures in aerospace engineering involve the comparison of computational fluid dynamics (CFD) data to experimental results from sources like wind tunnel tests. However, an incongruity exists between the data available from these sources: flow visualization is available by default in computational data, whereas in most experimental setups the available data is far more discrete and far more limited: integrated forces and moments, discrete pressure and temperature probes, etc. When differences exist between quantities of interest like lift and drag coefficients, the lack of full-field flow data from the experiments complicates most attempts to reconcile why the different data sources disagree. To this end, a shallow neural network, constrained by certain fluid flow properties, was trained to approximate flow field snapshots given only discrete data like that available in a wind tunnel test. The constructed snapshots, even for complex incompressible fluid flows, were found to agree at the large scales with the true flow fields. With this tool, researchers can more readily and easily understand why quantities of interest differ between their experimental and computational datasets. This in turn improves the resulting data's uncertainty measures.

Yury Lebedev↗

A Nowcasting Approach for Low Earth Orbit Hyperspectral Infrared Soundings Within the Convective Environment

Low Earth orbit (LEO) hyper-spectral infrared (IR) sounders have significant yet untapped potential for characterizing thermodynamic environments of convective initiation and ongoing convection. While LEO soundings are of value to weather forecasters, the temporal resolution needed to resolve the rapidly evolving thermodynamics of the convective environment is limited. We have developed a novel nowcasting methodology to extend snapshots of LEO soundings forward in time up to six hours to create a product available within National Weather Service systems for user assessment. Our methodology is based on parcel forward-trajectory calculations from the satellite observing time to generate future soundings of temperature (T) and specific humidity (q) at regularly gridded intervals in space and time. The soundings are based on NOAA-Unique Combined Atmospheric Processing System (NUCAPS) retrievals from the Suomi NPP and NOAA-20 satellite platforms. The tendencies of derived convective available potential energy (CAPE) and convective inhibition (CIN) are evaluated against gridded, hourly accumulated rainfall obtained from the Multi-Radar Multi-Sensor (MRMS) observations for 24 hand-selected cases over the Contiguous United States. Areas with forecast increases in CAPE (reduced CIN) are shown to be associated with areas of precipitation. The increases in CAPE and decreases in CIN are largest for areas that have the heaviest precipitation and are statistically significant compared to areas without precipitation. These results imply that adiabatic parcel advection of LEO satellite sounding snapshots forward in time are capable of identifying convective initiation over an expanded temporal scale compared to soundings used only during the LEO satellite overpass time.

North America↗

Modeling the Formation and Eruption of Coronal Structures by Linking Data-Driven Magnetofrictional and MHD Simulations for AR 12673

Context .The data-driven and time-dependent modeling of coronal magnetic fields is crucial for understanding solar eruptions. These efforts are complicated by the challenges of finding a balance between physical realism and computing efficiency. One possible technique is to couple two modeling approaches. Aims . Our aim here is to showcase our progress in using time-dependent magnetofrictional model (TMFM) results as input to dynamical magnetohydrodynamic (MHD) simulations. However, due to the different evolution processes in these two models, using TMFM snapshots in an MHD simulation is nontrivial. We address these issues, both physically and numerically, discuss the incompatibility of the TMFM output to serve as the initial condition in MHD simulations, and show our methods of mitigating this. The evolution of the flux systems and the cause of the eruption are investigated. Methods . TMFM is a prevalent approach that has proven to be a very useful tool in the study of the formation of unstable structures in the solar corona. In particular, it is capable of incorporating observational data as initial and boundary conditions and requires shorter computational time compared to MHD simulations. To leverage the efficiency of data-driven TMFM and also to simulate eruptive events in the MHD framework, one can apply TMFM up to a certain time before the expected eruption(s) and then proceed with the simulation in the full or ideal MHD regime in order to more accurately capture the eruption process. Results . We show the results of a benchmark test case with a linked TMFM and MHD simulation to study the evolution of NOAA active region 12673. A rise of a twisted flux bundle through the MHD simulation domain is observed, but we find that the rate of the rise and the altitude reached depends on the time of the TMFM snapshot that was used to initialize the MHD simulation and the helicity injected into the system. The analysis suggested that torus instability and slip-running reconnection could play an important role in the eruption. Conclusions . The results show that the linkage of TMFM and zero-β MHD models can be successfully used to model the eruptive coronal magnetic fields.

F. Daei↗

Matrix Completion Using Alternating Minimization for Distribution System State Estimation: Preprint

This paper examines the problem of state estimation in power distribution systems under low-observability conditions. The recently proposed constrained matrix completion method which combines the standard matrix completion method and power flow constraints has been shown to be effective in estimating voltage phasors under low-observability conditions using single-snapshot information. However, the method requires solving a semidefinite programming (SDP) problem, which becomes computationally infeasible for large systems and if multiple-snapshot (time-series) information is used. This paper proposes an efficient algorithm to solve the constrained matrix completion problem with time-series data. This algorithm is based on reformulating the matrix completion problem as a bilinear (non-convex) optimization problem, and applying the alternating minimization algorithm to solve this problem. This paper proves the summable convergence of the proposed algorithm, and demonstrates its efficacy and scalability via IEEE 123-bus system and a real utility feeder system. This paper also explores the value of adding more data from the history in terms of computation time and estimation accuracy.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Fiber optic sensing system for grid-based assets

A sensor system includes a sensor network comprising at least one optical fiber having one or more optical sensors. At least one of the optical sensors is arranged to sense vibration of an electrical device and to produce a time variation in light output in response to the vibration. A detector generates an electrical time domain signal in response to the time variation in light output. An analyzer acquires a snapshot frequency component signal which comprises one or more time varying signals of frequency components of the time domain signal over a data acquisition time period. The analyzer detects a condition of the electrical device based on the snapshot frequency component signal.

Kiesel, Peter↗

Independent malware detection architecture

A system and method (referred to as the system) detect malware by training a rule-based model, a functional based model, and a deep learning-based model from a memory snapshot of a malware free operating state of a monitored device. The system extracts a feature set from a second memory snapshot captured from an operating state of the monitored device and processes the feature set by the rule-based model, the functional-based model, and the deep learning-based model. The system identifies identifying instances of malware on the monitored device without processing data identifying an operating system of the monitored device, data associated with a prior identification of the malware, data identifying a source of the malware, data identifying a location of the malware on the monitored device, or any operating system specific data contained within the monitored device.

Smith, Jared M.↗

Fiber optic sensing system for grid-based assets

A sensor system includes a sensor network comprising at least one optical fiber having one or more optical sensors. At least one of the optical sensors is arranged to sense vibration of an electrical device and to produce a time variation in light output in response to the vibration. A detector generates an electrical time domain signal in response to the time variation in light output. An analyzer acquires a snapshot frequency component signal which comprises one or more time varying signals of frequency components of the time domain signal over a data acquisition time period. The analyzer detects a condition of the electrical device based on the snapshot frequency component signal.

Kiesel, Peter↗

Roadmap for Sustainable Mixed Ionic–Electronic Conducting Membranes

Mixed ionic-electronic conducting (MIEC) membranes have gained growing interest recently for various promising environmental and energy applications, such as H 2 and O 2 production, CO 2 reduction, O 2 and H 2 separation, CO 2 separation, membrane reactors for production of chemicals, cathode development for solid oxide fuel cells, solar-driven evaporation and energy-saving regeneration as well as electrolyzer cells for power-to-X technologies. The purpose of this roadmap, written by international specialists in their fields, is to present a snapshot of the state-of-the-art, and provide opinions on the future challenges and opportunities in this complex multidisciplinary research field. As the fundamentals of using MIEC membranes for various applications become increasingly challenging tasks, particularly in view of the growing interdisciplinary nature of this field, a better understanding of the underlying physical and chemical processes is also crucial to enable the career advancement of the next generation of researchers. As an integrated and combined article, it is hoped that this roadmap, covering all these aspects, will be informative to support further progress in academics as well as in the industry-oriented research toward commercialization of MIEC membranes for different applications.

36 MATERIALS SCIENCE↗

Multispectral Quantitative Phase Imaging Using a Diffractive Optical Network

As a label‐free imaging technique, quantitative phase imaging (QPI) provides optical path length information of transparent specimens for various applications in biology, materials science, and engineering. Multispectral QPI measures quantitative phase information across multiple spectral bands, permitting the examination of wavelength‐specific phase and dispersion characteristics of samples. Herein, the design of a diffractive processor is presented that can all‐optically perform multispectral quantitative phase imaging of transparent phase‐only objects within a snapshot. The design utilizes spatially engineered diffractive layers, optimized through deep learning, to encode the phase profile of the input object at a predetermined set of wavelengths into spatial intensity variations at the output plane, allowing multispectral QPI using a monochrome focal plane array. Through numerical simulations, diffractive multispectral processors are demonstrated to simultaneously perform quantitative phase imaging at 9 and 16 target spectral bands in the visible spectrum. The generalization of these diffractive processor designs is validated through numerical tests on unseen objects, including thin Pap smear images. Due to its all‐optical processing capability using passive dielectric diffractive materials, this diffractive multispectral QPI processor offers a compact and power‐efficient solution for high‐throughput quantitative phase microscopy and spectroscopy.

36 MATERIALS SCIENCE↗

An Atomic View of Cation Diffusion Pathways from Single‐Crystal Topochemical Transformations

Abstract The diffusion pathways of Li‐ions as they traverse cathode structures in the course of insertion reactions underpin many questions fundamental to the functionality of Li‐ion batteries. Much current knowledge derives from computational models or the imaging of lithiation behavior at larger length scales; however, it remains difficult to experimentally image Li‐ion diffusion at the atomistic level. Here, by using topochemical Li‐ion insertion and extraction to induce single‐crystal‐to‐single‐crystal transformations in a tunnel‐structured V 2 O 5 polymorph, coupled with operando powder X‐ray diffraction, we leverage single‐crystal X‐ray diffraction to identify the sequence of lattice interstitial sites preferred by Li‐ions to high depths of discharge, and use electron density maps to create a snapshot of ion diffusion in a metastable phase. Our methods enable the atomistic imaging of Li‐ions in this cathode material in kinetic states and provide an experimentally validated angstrom‐level 3D picture of atomic pathways thus far only conjectured through DFT calculations.

Handy, Joseph V.↗

Does Selectivity of Molecular Catalysts Change with Time? Polymerization Imaged by Single‐Molecule Spectroscopy

Abstract The chemoselectivity of molecular catalysts underpins much of modern synthetic organic chemistry. However, little is known about the selectivity of individual catalysts because this single‐catalyst‐level behavior is hidden by the bulk catalytic behavior. Here, for the first time, the selectivity of individual molecular catalysts for two different reactions is imaged in real time at the single‐catalyst level. This imaging is achieved through fluorescence microscopy paired with spectral probes that produce a snapshot of the instantaneous chemoselectivity of a single catalyst for either a single‐chain‐elongation or a single‐chain‐termination event during ruthenium‐catalyzed polymerization. Superresolution imaging of multiple selectivity events, each at a different single‐molecular ruthenium catalyst, indicates that catalyst selectivity may be unexpectedly spatially and time‐variable.

Garcia, IV, Antonio↗

Characterization of a Molecule Partially Confined at the Pore Mouth of a Zeotype

Abstract We investigate the interaction between a molecule and a pore mouth—a critical step in adsorption processes—by characterizing the conformation of a macrocyclic calix[4]arene‐Ti IV complex, which is grafted on the external surface of a zeotype (*‐SVY). X‐ray absorption and 13 C{ 1 H} CPMAS NMR spectroscopies independently detect a unique conformation of this complex when it is grafted at crystallographically equivalent locations that lie at the interface of 7 Å hemispherical microporous cavities and the external surface. Electronic structure calculations support the presence of this unique conformation, and suggest that it is brought about by a specific orientation of the macrocycle that maximizes non‐covalent interactions between calix[4]arene upper‐rim tert ‐butyl substituents and the microporous‐cavity walls. Our comparative study provides a rare “snapshot” of a molecule partially confined at a pore mouth, an essential intermediate for adsorption into micropores, and demonstrates how surrounding environment controls this confinement in a sensitive fashion.

Grosso‐Giordano, Nicolás A.↗