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River Delta Morphotypes Emerge From Multiscale Characterization of Shorelines
Abstract Delta shoreline structure has long been hypothesized to encode information on the relative influence of fluvial, wave, and tidal processes on delta formation and evolution. We introduce here a novel multiscale characterization of shorelines by defining three process‐informed morphological metrics. We show that this characterization yields self‐emerging classes of morphologically similar deltas, that is, delta morphotypes, and also predicts the dominant forcing of each morphotype. Then we show that the dominant forcings inferred from shoreline structure generally align with those estimated via relative sediment fluxes, while positing that misalignments arise from spatiotemporal heterogeneity in deltaic sediment fluxes not captured in their estimates. The proposed framework for shoreline characterization advances our quantitative understanding of how shoreline features reflect delta forcings, and may aid in deciphering paleoclimate from images of ancient deposits and projecting delta morphologic response to changes in sediment fluxes.
Adapted Cell Design for the Operando X‑Ray Absorption Study of a Structurally Evolving Cu Nanoparticle Ensemble during the CO2 Electroconversion to Multicarbon Products
An improved understanding of the materials that will sustain the future of energy production, storage, and delivery calls for better characterization tools. Operando characterization methods have thus become essential for investigating electrocatalytic materials. Without their resulting insights, the study of highly performing catalysts post-mortem cannot viably facilitate the further development of functional catalysts. Herein, we present an operando electrochemical cell designed for hard X-ray absorption spectroscopy (XAS) and specifically adapted to the study of an electrocatalytically active Cu nanoparticle ensemble. So far, this nanocatalyst has proven to pose quite a challenge to characterize due to its unique structural dynamics. Adopting a design comparable to the H-cell employed for all activity testing, we report the satisfactory translation of the active site formation into an XAS-compatible cell. The simultaneous collection of CO2-derived products during XAS characterization enabled the operando characterization of this CO2-reducing active structure. We report a Cu–Cu coordination number of the first scattering path higher than suggested in our previous studies, highlighting the importance of monitoring metastable nanoelectrocatalysts in operando. This study illustrates important caveats for the electrocatalysis community when considering the application of operando XAS. Our results highlight that the sample size, homogeneity, and stability determine how to interpret the measured signal. Considering these parameters carefully, the operando EXAFS results confirm the exceptional undercoordinated character of the Cu nanoparticle ensemble during CO2 reduction to C2+ products.
The Local Electronic Structure of Supercritical CO 2 from X-ray Raman Spectroscopy and Atomistic-Scale Modeling
Supercritical CO 2 is encountered in several technical and natural systems related to biology, geophysics, and engineering. While the structure of gaseous CO 2 has been studied extensively, the properties of supercritical CO 2 , particularly close to the critical point, are not well-known. Here, in this work, we combine X-ray Raman spectroscopy, molecular dynamics simulations, and first-principles density functional theory (DFT) calculations to characterize the local electronic structure of supercritical CO 2 at conditions around the critical point. The X-ray Raman oxygen K-edge spectra manifest systematic trends associated with the phase change of CO 2 and the intermolecular distance. Extensive first-principles DFT calculations rationalize these observations on the basis of the 4sσ Rydberg state hybridization. X-ray Raman spectroscopy is found to be a sensitive tool for characterizing electronic properties of CO 2 under challenging experimental conditions and is demonstrated to be a unique probe for studying the electronic structure of supercritical fluids.
Simulating excited-state complex ensembles: Fluorescence and solvatochromism in amine-arene exciplexes
Exciplexes are excited-state complexes formed as a result of partial charge transfer from the donor to the acceptor species when one moiety of the donor–acceptor pair is electronically excited. The arene–amine exciplex formed between oligo-(p-phenylene) (OPP) and triethylamine (TEA) is of interest in the catalytic photoreduction of CO2 because it can compete with complete electron transfer to the OPP catalyst. Therefore, formation of the exciplex can hinder the generation of a radical anion OPP·− necessary for subsequent CO2 reduction. We report an implementation of a workflow automating quantum-chemistry calculations that generate and characterize an ensemble of structures to represent this exciplex state. We use FireWorks, Pymatgen, and Custodian Python packages for high-throughput ensemble generation. The workflow includes time-dependent density functional theory optimization, verification of excited-state minima, and exciplex characterization with natural transition orbitals, exciton analysis, excited-state Mulliken charges, and energy decomposition analysis. Fluorescence spectra computed for these ensembles using Boltzmann-weighted contributions of each structure agree better with experiment than our previous calculations based on a single representative exciplex structure [Kron et al., J. Phys. Chem. A 126, 2319–2329 (2022)]. The ensemble description of the exciplex state also reproduces an experimentally observed red shift of the emission spectrum of [OPP-4–TEA]* relative to [OPP-3–TEA]*. The workflow developed here streamlines otherwise labor-intensive calculations that would require significant user involvement and intervention.
Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO) 5
Excitation of iron pentacarbonyl [Fe(CO) 5 ], a prototypical photocatalyst, at 266 nm causes the sequential loss of two CO ligands in the gas phase, creating catalytically active, unsaturated iron carbonyls. Despite numerous studies, major aspects of its ultrafast photochemistry remain unresolved because the early excited-state dynamics have so far eluded spectroscopic observation. This has led to the long-held assumption that ultrafast dissociation of gas-phase Fe(CO) 5 proceeds exclusively on the singlet manifold. Herein, we present a combined experimental–theoretical study employing ultrafast extreme ultraviolet transient absorption spectroscopy near the Fe M 2,3 -edge, which features spectral evolution on 100 fs and 3 ps time scales, alongside high-level electronic structure theory, which enables characterization of the molecular geometries and electronic states involved in the ultrafast photodissociation of Fe(CO) 5 . We assign the 100 fs evolution to spectroscopic signatures associated with intertwined structural and electronic dynamics on the singlet metal-centered states during the first CO loss and the 3 ps evolution to the competing dissociation of Fe(CO) 4 along the lowest singlet and triplet surfaces to form Fe(CO) 3 . Calculations of transient spectra in both singlet and triplet states as well as spin–orbit coupling constants along key structural pathways provide evidence for intersystem crossing to the triplet ground state of Fe(CO) 4 . Finally, our work presents the first spectroscopic detection of transient excited states during ultrafast photodissociation of gas-phase Fe(CO) 5 and challenges the long-standing assumption that triplet states do not play a role in the ultrafast dynamics.
Pseudomonas aeruginosa Dps (PA0962) Functions in H 2 O 2 Mediated Oxidative Stress Defense and Exhibits In Vitro DNA Cleaving Activity
We report the structural, biochemical, and functional characterization of the product of gene PA0962 from Pseudomonas aeruginosa PAO1. The protein, termed Pa Dps, adopts the Dps subunit fold and oligomerizes into a nearly spherical 12-mer quaternary structure at pH 6.0 or in the presence of divalent cations at neutral pH and above. The 12-Mer Pa Dps contains two di-iron centers at the interface of each subunit dimer, coordinated by conserved His, Glu, and Asp residues. In vitro, the di-iron centers catalyze the oxidation of Fe 2+ utilizing H 2 O 2 (not O 2 ) as an oxidant, suggesting Pa Dps functions to aid P. aeruginosa to survive H 2 O 2 -mediated oxidative stress. In agreement, a P. aeruginosa Δdps mutant is significantly more susceptible to H 2 O 2 than the parent strain. The Pa Dps structure harbors a novel network of Tyr residues at the interface of each subunit dimer between the two di-iron centers, which captures radicals generated during Fe 2+ oxidation at the ferroxidase centers and forms di-tyrosine linkages, thus effectively trapping the radicals within the Dps shell. Surprisingly, incubating Pa Dps and DNA revealed unprecedented DNA cleaving activity that is independent of H 2 O 2 or O 2 but requires divalent cations and 12-mer Pa Dps.
Magneto-structural and induction heating properties of MFe2O4 (M?=?Co, Mn, Zn) MNPs for magnetic particle hyperthermia application
The thermal decomposition approach was used for the synthesis of MFe2O4 magnetic nanoparticles (MNPs) by substituting M as Co, Mn, and Zn. The obtained MNPs were characterized for magneto-structural properties using X-Ray diffraction patterns, FTIR, Raman and Mossbauer spectroscopy techniques which confirm the formation of phase pure cubic spinel ferrite with space group Fd3m and five Raman active modes. The size, morphology, and compositional analysis was performed using HRTEM and EDX where the size of MNPs was found to be less than 10 nm that attains superparamagnetism. The magnetic hyperthermia performance of obtained MNPs was evaluated by induction heating experiments at magnetic field range 13.3 to 26.7 kAm-1. The specific absorption rate (SAR) and intrinsic loss power (ILP) values were determined at different magnetic fields within the human tolerable range and correlated with magneto-structural properties to evaluate its potential for possible magnetic particle hyperthermia therapy.
Quasiparticle electronic structure of phthalocyanine:TMD interfaces from first-principles GW
Interfaces formed between monolayer transition metal dichalcogenides and (metallo)phthalocyanine molecules are promising in energy applications and provide a platform for studying mixed-dimensional molecule-semiconductor heterostructures in general. An accurate characterization of the frontier energy level alignment at these interfaces is key in the fundamental understanding of the charge transfer dynamics between the two photon absorbers. Here, we employ the first-principles substrate screening GW approach to quantitatively characterize the quasiparticle electronic structure of a series of interfaces: metal-free phthalocyanine (H 2 Pc) adsorbed on monolayer MX 2 (M = Mo, W; X = S, Se) and zinc phthalocyanine (ZnPc) adsorbed on MoX 2 (X = S, Se). Furthermore, we reveal the dielectric screening effect of the commonly used α-quartz (SiO 2 ) substrate on the H 2 Pc:MoS 2 interface using the dielectric embedding GW approach. Our calculations furnish a systematic set of GW results for these interfaces, providing the structure–property relationship across a series of similar systems and benchmarks for future experimental and theoretical studies.
Population genomics and history of speciation reveal fishery management gaps in two related redfish species ( Sebastes mentella and Sebastes fasciatus )
Abstract Understanding the processes shaping population structure and reproductive isolation of marine organisms can improve their management and conservation. Using genomic markers combined with estimation of individual ancestries, assignment tests, spatial ecology, and demographic modeling, we (i) characterized the contemporary population structure, (ii) assessed the influence of space, fishing depth, and sampling years on contemporary distribution, and (iii) reconstructed the speciation history of two cryptic redfish species, Sebastes mentella and S. fasciatus . We genotyped 860 individuals in the Northwest Atlantic Ocean using 24,603 filtered single nucleotide polymorphisms (SNPs). Our results confirmed the clear genetic distinctiveness of the two species and identified three ecotypes within S. mentella and five populations in S. fasciatus . Multivariate analyses highlighted the influence of spatial distribution and depth on the overall genomic variation, while demographic modeling revealed that secondary contact models best explained inter‐ and intragenomic divergence. These species, ecotypes, and populations can be considered as a rare and wide continuum of genomic divergence in the marine environment. This acquired knowledge pertaining to the evolutionary processes driving population divergence and reproductive isolation will help optimizing the assessment of demographic units and possibly to refine fishery management units.
Estimation of elastic properties of an additively manufactured lattice using resonant ultrasound spectroscopy
Development of improved approaches in the characterization of additively manufactured structures continues to be a topic of interest for the advanced manufacturing community. This article will investigate an approach using resonant ultrasound spectroscopy (RUS) to determine the effective elastic constants of an orthotropic lattice structure. The evaluation is performed on a cube shaped 316 L stainless steel test specimen, constructed using selective laser melting techniques. The approach uses RUS techniques in conjunction with the assumption that in the frequency regime of interest, the wavelength of the diagnostic ultrasound is greater than the discrete structural features of the unit cell of the lattice; thus, the AM structure can be treated as an anisotropic continuum with effective material properties and symmetry inherited from the unit cell. The RUS analysis estimates the nine elastic coefficients associated with orthotropic sample symmetry, which, in turn, are used to determine the elastic moduli and Poisson ratios. Current results show good agreement between experiments and modeled data. Comparisons to published results are also in good agreement, indicating the potential applicability of this characterization technique for estimating the linear elastic properties of innovative additive manufactured metal lattice structures.
Understanding the Photochemical Properties of Polythiophene Polyelectrolyte Soft Aggregates with Sodium Dodecyl Sulfate for Antimicrobial Activity
The threat of antibiotic-resistant bacteria is an ever-increasing problem in public health. In this report, we examine the photochemical properties with a proof-of-principle biocidal assay for a novel series of regio-regular imidazolium derivative poly-(3-hexylthiophene)/sodium dodecyl sulfate (P3HT-Im/SDS) materials from ultrafast sub-ps dynamics to μs generation of reactive oxygen species (ROS) and 30 min biocidal reactivity with Escherichia coli (E. coli). This broad series encompassing pure P3HT-Im to cationic, neutral, and anionic P3HT-Im/SDS materials are all interrogated by a variety of techniques to characterize the physical material structure, electronic structure, and antimicrobial activity. Our results show that SDS complexation with P3HT-Im results in aggregate materials with reduced ROS generation and light-induced anti-microbial activity. However, our characterization reveals that the presence of non-aggregated or lightly SDS-covered polymer segments is still capable of ROS generation. Full encapsulation of the P3HT-Im polymer completely deactivates the light killing pathway. High SDS concentrations, near and above critical micelle concentration, further deactivate all anti-microbial activity (light and dark) even though the P3HT-Im regains its electronic properties to generate ROS.
Reviewing and Exploring the Qualitative Impacts That Different Market and Regulatory Measures Can Have on Encouraging Energy Communities Based on Their Organizational Structure
The emergence of energy communities represents a promising option to democratize the energy system by empowering consumers to take a more active role. This can aid in achieving energy and environmental goals as well as encouraging more equitable distribution of costs and revenues between all parties on the energy system. Despite this potential, energy communities are still a nascent solution, the success of which is heavily influenced by regulations. As a result, there are a wide variety of organizational structures for energy communities at this time. This paper provides a review of the policy landscape in Spain as it relates to energy communities. This work also presents a formalized method for characterizing different energy community structures and provides a qualitative assessment of the impacts of different measures to encourage energy communities with respect to their organizational structure. Findings suggest that many market-focused measures, including wholesale, local flexibility, capacity, and multisector market measures favor larger, more integrated communities, while regulatory, legal, and organizational measures, including peer-to-peer trading, aggregation, and self-consumption favor smaller, more distributed communities. Additionally, when developing policies to encourage the growth of energy communities, policymakers should be cognizant of the progression of policies in the context of the desired outcomes for energy community growth specific to the region or country and its goals.
Jackson, L., Johnson, M.B., Latrach, A., Grimes, D., Martinez, C., and Mclaughlin, J.F., 2024, Multidisciplinary geotechnical data collection, curation, and analysis for conformity with the regulatory framework for geologic carbon storage in Wyoming, USA: Geological Society of America Abstracts with Programs. Vol. 56, No. 5, 2024, doi: 10.1130/abs/2024AM-405024
Title: Multidisciplinary Geotechnical Data Collection, Curation, and Analysis for Conformity with the Regulatory Framework for Geologic Carbon Storage in Wyoming, USA. Text: Construction and operation of wells for geologic sequestration of carbon dioxide necessitate that they are permitted under the Environmental Protection Agency’s Underground Injection Control Class VI requirements. Class VI wells conform to stringent requirements to ensure long-term safety and integrity of the storage site and the protection of Underground Sources of Drinking Water. Entities pursuing Class VI permitting must provide comprehensive geologic site characterization, including regional geologic structure and stratigraphy, aquifer information, reservoir and confining unit geomechanical properties, geochemical analyses, assessment of trapping capacity and mechanisms, and a variety of other of multidisciplinary geotechnical data. The Wyoming Class VI Site Characterization Database Project is focused on developing a geologic site characterization database of geotechnical information, which has been compiled and verified from established, public databases/entities and scientific literature to expedite Class VI permitting in Sweetwater County within the Greater Green River Basin of southern Wyoming. The preliminary suite of compiled data from 14,000 wells includes 8,000 wells with logs and 7,250 wells with formation tops, ~70 wells with core data (e.g., X-Ray diffraction, petrographic, and petrophysical data), ~2,500 water analyses, ~740 seismic events data, and ~520 bottom-hole temperature measurements. Future work on—and stemming from—this project will include new core analyses, calculation and interpolation of subsurface temperature gradients, mechanical earth models, geochemical simulations, storage capacity estimation, stratigraphic column generation and correlation, and construction of subsurface maps. Finally, this work will help to inspire and facilitate subsurface data compilation and curation beyond Sweetwater County, Wyoming.
The Resilience Planning Landscape for Communities and Electric Utilities
Synapse Energy Economics has conducted structured interviews to better characterize the current landscape of resilience planning within and across jurisdictions. Synapse interviewed representatives of a diverse group of communities and their electric utilities. The resulting case studies span geographies and utility regulatory structures and represent a range of threats. They also vary in terms of population density and size. This report summarizes our approach and the findings gleaned from these conversations. All the communities and utilities we interviewed see increased interest in and commitment of resources for energy-related resilience. The risks and consequences these communities and utilities faced in the past, face now, and will face in the future drove them to improve engagement, advance processes, further decision-making, and in many cases invest in projects. While no process used by communities and utilities was the same, the different processes used by communities and utilities allowed each one to make progress in its own way. Several approaches are emerging that can provide good models for other communities and utilities with an interest in improving resilience.
Copper-nickel electroplating of 3D-printed acrylonitrile butadiene styrene for interference and radiation shielding applications
Here, in this study, electromagnetic and radiation shielding structures were fabricated by 3D printing acrylonitrile butadiene styrene (ABS) structures via fused filament fabrication and electroplating with copper (Cu) and nickel (Ni) metals. Prior to electroplating, the printed ABS materials were made conductive by surface electrodeposition of polypyrrole (PPy). ABS adsorbs the pyrrole monomer, which subsequently polymerizes via oxidation forming conductive PPy layer on the printed structures. The successful anchoring of PPy layer can be attributed to its hydrogen bonding and electrostatic interactions with ABS. Thermal analysis, optical, and electron microscopy equipped with energy dispersive X-ray were employed to characterize the printed shielding structures, while the interference and radiation shielding effectiveness were evaluated using a spectrum analyzer and dosimeter, respectively. The interference shielding was found to be effective at 60 ± 5 dB over relatively small frequency range. Shielding was also apparent against gamma and X-ray ionizing rays, but more significantly effective against beta rays. Furthermore, the Cu/Ni coating was able to reduce any heat-induced dimensional changes for the 3D printed ABS substrate without compromising the mechanical integrity.
Tuning Metal–Organic Framework (MOF) Topology by Regulating Ligand and Secondary Building Unit (SBU) Geometry: Structures Built on 8-Connected M 6 (M = Zr, Y) Clusters and a Flexible Tetracarboxylate for Propane-Selective Propane/Propylene Separation
Topology evolution originating from variations of linker and SBU (Secondary Building Unit) geometries could largely enrich the chemistry of metal–organic frameworks (MOFs). Here we report the synthesis and characterization of three MOF structures built on the same organic linker, N,N,N',N'-Tetrakis(4-carboxyphenyl)-1,4-phenylenediamine (tcppda) and similar 8-connected M 6 (M = Zr or Y) clusters. The three compounds, HIAM-402, HIAM-403, and HIAM-311, feature 4,8-connected sqc, scu, and flu topology, respectively. Detailed structural analysis revealed that different geometries of the inorganic M 6 SBUs as well as the organic linker have led to the formation of distinct MOF nets. In particular, HIAM-402 features exceptional framework stability and high porosity and acts as a propane-selective adsorbent for the discrimination of propane and propylene. Its balanced adsorption selectivity (S propane/propylene = 1.43) and capacity (Q propane = 133.3 cm 3 /g, 298 K and 1 bar) endow it with the capability of separating propane and propylene mixtures and one-step production of highly pure propylene (purity >99.9%), as validated by column breakthrough measurements, with the presence of moisture or propyne. As a result, ab initio calculations further confirm that the propane-selective behavior of HIAM-402 is a result of its higher binding energy toward propane compared to that of propylene.
3D structures and methods therefor
Aspects of the disclosure are directed to methods and/or apparatuses involving one or more of a conductive polymer, deposition of a conductive polymer and 3D (three-dimensional) printing of a continuous bead of material. As may be implemented in accordance with one or more embodiments characterized herein, a 3D structure is formed as follows. A stacked layer is formed by depositing a continuous bead of material along an uninterrupted path that defines a first layer of the 3D structure. A sidewall of the 3D structure is formed with opposing surfaces respectively defined by successive stacked layers of the 3D structure by, for each stacked layer (including the first layer), depositing the continuous bead of material along the path and with a surface thereof in contact with a surface of the continuous bead of material of an adjacent one of the stacked layers.