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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.

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At least 37 records · Page 2

Resonant Tender X-ray Scattering for Disclosing the Backbone Conformation of Conjugated Polymers

The backbone conformation of conjugated polymers (CPs) is essential to their performance in electronic applications. Contrast-variation small-angle neutron scattering (CV-SANS) techniques were used to assess the CP’s backbone conformation, which relies on synthesis of deuterated polymers. Such a technique has been proven mature and effective. One drawback is that deuteration labeling might subtly alter polymer’s physical properties due to structural modifications. To address these challenges, we introduce a novel approach utilizing tender Xray scattering near the sulfur K-edge to distinctly evaluate the backbone versus whole chain conformation for a low-bandgap donor−acceptor CP, poly[(5,6-difluoro- 2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-dialkyl-2,2′;5′,2″;5″,2‴-quaterthiophen-5,5‴- diyl)] (PffBT4T). For PffBT4T dissolved in trimethylbenzene (TMB), the sulfur K-edge is identified at approximately 2477 eV using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Tender X-ray scattering conducted at presulfur K-edge and on-sulfur K-edge at elevated temperatures facilitated the distinction between the backbone and whole chain conformations. The results demonstrate that for highly flexible polymer, the backbone’s persistence length could be lower than that of the whole chains, suggesting a more flexible backbone. This rapid, label-free method enhances our ability to characterize CP’s backbone conformation efficiently, offering significant implications for the design and optimization of CPs for advanced electronics.

36 MATERIALS SCIENCE↗

Unmasking the Conformational Stability and Inhibitor Binding to SARS-CoV-2 Main Protease Active Site Mutants and Miniprecursor

We recently demonstrated that inhibitor binding reorganizes the oxyanion loop of a monomeric catalytic domain of SARS CoV-2 main protease (MPro) from an unwound (E) to a wound (active, E*) conformation, independent of dimerization. Here we assess the effect of the flanking N-terminal residues, to imitate the MPro precursor prior to its autoprocessing, on conformational equilibria rendering stability and inhibitor binding. Thermal denaturation (T m ) of C145A mutant, unlike H41A, increases by 6.8 °C, relative to wild-type mature dimer. An inactivating H41A mutation to maintain a miniprecursor containing TSAVL[Q or E] of the flanking nsp4 sequence in an intact form [ (-6) MPro H41A and (-6*) MPro H41A , respectively], and its corresponding mature MPro H41A were systematically examined. While the H41A mutation exerts negligible effect on T m and dimer dissociation constant (K dimer ) of MPro H41A , relative to the wild type MPro, both miniprecursors show a 4–5 °C decrease in T m and > 85-fold increase in K dimer as compared to MPro H41A . The K d for the binding of the covalent inhibitor GC373 to (-6*) MPro H41A increases ~12-fold, relative to MPro H41A , concomitant with its dimerization. While the inhibitor-free dimer exhibits a state in transit from E to E* with a conformational asymmetry of the protomers’ oxyanion loops and helical domains, inhibitor binding restores the asymmetry to mature-like oxyanion loop conformations (E*) but not of the helical domains. Finally, disorder of the terminal residues 1–2 and 302–306 observed in both structures suggest that N-terminal autoprocessing is tightly coupled to the E-E* equilibrium and stable dimer formation.

59 BASIC BIOLOGICAL SCIENCES↗

D–MOPH–25: diverse MOF–molecule pairs for Henry’s constants prediction

Computational methods like grand-canonical Monte Carlo simulations and machine learning (ML) have accelerated metal–organic frameworks (MOF) exploration but are typically limited to a narrow range of adsorbates due to data availability and force field constraints. In this study, we introduce a dataset of diverse MOF–molecule pairs for Henry’s constant prediction, D–MOPH–25, which systematically explores a diverse chemical space by combining 113 molecular adsorbates with over 5000 MOF structures through an active learning process. D–MOPH–25 constitutes the most diverse adsorbate dataset used in any ML study of molecular adsorption in MOFs to date. Our workflow builds a benchmark for predicting Henry’s constants at 300 K, leveraging conformal prediction for uncertainty quantification. Assessment through Shannon entropy and uniform manifold approximation and projection confirms the comprehensiveness of D–MOPH–25 while highlighting the importance of robust classification to filter out unphysical data points in regression tasks. Although future enhancements in model architecture and sampling criteria could improve predictive performance, our dataset already spans the target space using only 2.31% of total possibilities. This comprehensive dataset facilitates assessment of model generalizability across adsorbate species and can establish a foundation for high-throughput MOF screening and ML-driven separation processes.

active learning↗

Integrated Environmental Management System Communication at Large Sites - 20480

At a large Department of Energy-owned (DOE) site, there are challenges to communicating Environmental Management System (EMS) topics effectively. With multiple contractors and Environmental Management System scopes, as well as a large number of employees, communication preferences and possibilities vary, providing both the benefit and the challenge of differing pathways for sharing information. Additionally, data collection for site-wide environmental reporting involves numerous points of contact spread across contractors and requires organization and integrated communication. Focusing on the value of communication to enhance EMS education and awareness to drive environmental performance, we discuss the communication methods used both at a site-wide level and by individual organizations. Example methods include site-wide working group meetings, internal Share Point, site-wide surveys, collaborative reporting, weekly newsletters, and combined communication efforts with the Integrated Safety Management System (ISMS). Using external audit results to gauge employee environmental awareness and culture, we analyze the effectiveness of EMS communications. In conclusion, integration of EMS communication in alignment with the ISMS has assisted in meeting International Organization of Standardization 14001 (ISO 14001) requirements and strengthened the concept that environmental protection is part of safety for workers and the site. Increased environmental enthusiasm and awareness supports the effectiveness of EMS communication methods and positive external audit results. These results benefit other sites with EMS to gain knowledge of integrated communication efforts that increase the effectiveness of the EMS, environmental performance, and conformance with ISO 14001. By assessing the effectiveness of actual EMS communication methods, contractors will be able to take away tools to enhance environmental communication in their workplace. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A curated benchmark for cofolding models on kinase conformational states

Abstract Protein kinases are critical drug targets, requiring therapeutics that can modulate their active and inactive conformational states. While cofolding models can generate global folds directly from kinase sequences and ligand SMILES strings, these models have not yet been tested on their ability to recover ligand-induced-fit conformational states of the kinase proteins. Here, we introduce KinConfBench, a curated benchmark of 2225 high-quality human kinase chains to evaluate the ability of four state-of-the-art cofolding models—Boltz-2, Chai-1, Protenix, and RoseTTAFold-All-Atom—to recover both canonical and rare conformational states. We show that geometric success metrics of a ligand pose in the active site do not correlate strongly with the correct kinase conformational state, motivating a new set of dynamical benchmarks for assessing cofolding models. While all four cofolding models achieve ~60–80% prediction accuracy for kinase conformational classification, they exhibit severe mode collapse when performing multiple inferences, show negligible structural diversity in sampling induced-fit motions, and display a prevalent “apo-drift” in which most cofolding models predominantly predict the kinase to be in its ligand-free state. Our results highlight that capturing ligand-induced protein conformational diversity, not just geometric fit, is critical for next-generation structure-based drug discovery.

Sun, Kunyang↗

Mixed-flow design for microfluidic printing of two-component polymer semiconductor systems

The rational creation of two-component conjugated polymer systems with high levels of phase purity in each component is challenging but crucial for realizing printed soft-matter electronics. Here, we report a mixed-flow microfluidic printing (MFMP) approach for two-component π -polymer systems that significantly elevates phase purity in bulk-heterojunction solar cells and thin-film transistors. MFMP integrates laminar and extensional flows using a specially microstructured shear blade, designed with fluid flow simulation tools to tune the flow patterns and induce shear, stretch, and pushout effects. This optimizes polymer conformation and semiconducting blend order as assessed by atomic force microscopy (AFM), transmission electron microscopy (TEM), grazing incidence wide-angle X-ray scattering (GIWAXS), resonant soft X-ray scattering (R-SoXS), photovoltaic response, and field effect mobility. For printed all-polymer (poly[(5,6-difluoro-2-octyl-2H-benzotriazole-4,7-diyl)-2,5-thiophenediyl[4,8-bis[5-(2-hexyldecyl)-2-thienyl]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]-2,5-thiophenediyl]) [J51]:(poly{[N,N′-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)}) [N2200]) solar cells, this approach enhances short-circuit currents and fill factors, with power conversion efficiency increasing from 5.20% for conventional blade coating to 7.80% for MFMP. Moreover, the performance of mixed polymer ambipolar [poly(3-hexylthiophene-2,5-diyl) (P3HT):N2200] and semiconducting:insulating polymer unipolar (N2200:polystyrene) transistors is similarly enhanced, underscoring versatility for two-component π -polymer systems. Mixed-flow designs offer modalities for achieving high-performance organic optoelectronics via innovative printing methodologies.

42 ENGINEERING↗

Assessment of enzyme active site positioning and tests of catalytic mechanisms through X-ray–derived conformational ensembles

How enzymes achieve their enormous rate enhancements remains a central question in biology, and our understanding to date has impacted drug development, influenced enzyme design, and deepened our appreciation of evolutionary processes. While enzymes position catalytic and reactant groups in active sites, physics requires that atoms undergo constant motion. Numerous proposals have invoked positioning or motions as central for enzyme function, but a scarcity of experimental data has limited our understanding of positioning and motion, their relative importance, and their changes through the enzyme’s reaction cycle. To examine positioning and motions and test catalytic proposals, we collected “room temperature” X-ray crystallography data for Pseudomonas putida ketosteroid isomerase (KSI), and we obtained conformational ensembles for this and a homologous KSI from multiple PDB crystal structures. Here, ensemble analyses indicated limited change through KSI’s reaction cycle. Active site positioning was on the 1- to 1.5-Å scale, and was not exceptional compared to noncatalytic groups. The KSI ensembles provided evidence against catalytic proposals invoking oxyanion hole geometric discrimination between the ground state and transition state or highly precise general base positioning. Instead, increasing or decreasing positioning of KSI’s general base reduced catalysis, suggesting optimized Ångstrom-scale conformational heterogeneity that allows KSI to efficiently catalyze multiple reaction steps. Ensemble analyses of surrounding groups for WT and mutant KSIs provided insights into the forces and interactions that allow and limit active-site motions. Most generally, this ensemble perspective extends traditional structure–function relationships, providing the basis for a new era of “ensemble–function” interrogation of enzymes.

59 BASIC BIOLOGICAL SCIENCES↗

Dynamic risk assessment for geologic CO 2 sequestration

At a geologic CO 2 sequestration (GCS) site, geologic uncertainty usually leads to large uncertainty in the predictions of properties that influence metrics for leakage risk assessment, such as CO 2 saturations and pressures in potentially leaky wellbores, CO 2 /brine leakage rates, and leakage consequences such as changes in drinking water quality in groundwater aquifers. The large uncertainty in these risk-related system properties and risk metrics can lead to over-conservative risk management decisions to ensure safe operations of GCS sites. The objective of this work is to develop a novel approach based on dynamic risk assessment to effectively reduce the uncertainty in the predicted risk-related system properties and risk metrics. We demonstrate our framework for dynamic risk assessment on two case studies: a 3D synthetic example and a synthetic field example based on the Rock Springs Uplift (RSU) storage site in Wyoming, USA. Results show that the U.S. National Risk Assessment Partnership’s Open Source Integrated Assessment Model (NRAP-Open-IAM) coupled with a conformance evaluation can be used to effectively quantify and reduce the uncertainty in the predictions of risk-related system properties and risk metrics in GCS.

58 GEOSCIENCES↗

Computational Tools and Workflows for Quantitative Risk Assessment and Decision Support for Geologic Carbon Storage Sites: Progress and Insights from the U.S. DOE’s National Risk Assessment Partnership

The 2005 Intergovernmental Panel on Climate Change (IPCC) Special Report on CCS raised the profile of CO2 capture and storage (CCS) as an important technology for reducing greenhouse gas (GHG) emissions. CCS is now recognized as a key component of most climate change mitigation scenarios. Since publication of that report the international research, development, and deployment (RD&D) community has advanced key technical aspects, clarified regulatory requirements, explored value chain and infrastructure solutions, and developed incentive paradigms to enable and promote large-scale deployment of CCS. These efforts have included research to better characterize geologic storage resources, to improve injection performance and storage efficiency, to assess and manage subsurface environmental risks, and to advance monitoring technologies to assure system conformance. These efforts have helped to build confidence in the viability of geologic carbon storage (GCS), but stakeholder concerns about long-term risks and liability associated with GCS remain a hurdle to broad acceptance and large-scale deployment of CCS. Since 2010, the U.S. DOE’s National Risk Assessment Partnership (NRAP) – a research collaboration between five contributing national laboratories – has worked to establish and demonstrate methods and tools to quantify and manage the subsurface environmental risks associated with GCS, amidst uncertainty. This work supports the Office of Fossil Energy and Carbon Management Carbon Transport and Storage Program’s goal of advancing safe and secure commercial-scale GCS deployment. To address the technical challenge of simulating the physical response of the GCS site to large-scale CO2 injection, NRAP has adopted an approach that relies on coupling computationally efficient reduced-order and/or data-driven proxy models of important system components (i.e., storage reservoir, sealing caprock, leakage pathways, intermediate formations, overlying groundwater aquifers, and the atmosphere) in integrated assessment framework. That integrated model of the physical system is complemented with fit-for purpose functionality to support site characterization and risk-related decisions. The recently released NRAP Phase II toolset includes the Open-Source Integrated Assessment Model (NRAP-Open-IAM) for evaluation of trends in leakage risk and potential impact, tools to support monitoring design optimization (Designs for Risk Evaluation and Management – DREAM v3.0 and Passive Seismic Monitoring Tool - PSMT), and tools for state of stress evaluation (State-of-Stress Analysis Tool - SOSAT) and forecasting induced seismicity risk. The NRAP team has also released a pair of reports describing conceptual workflows to incorporate physics-based, quantitative risk assessment into many of the design, planning, operation, and closure decisions for GCS projects. An online catalogue highlights published studies where these tools and methods are demonstrated. In this presentation, the utility of these products to assess risks and address key stakeholder questions will be highlighted through examples, and related insights about the safety and security of geologic carbon storage in qualified storage sites will be discussed. The prospect of rapid, large-scale deployment of GCS technology to aggressively reduce anthropogenic CO2 emissions requires careful consideration of interference between multiple commercial-scale storage projects within a basin. Going forward, NRAP is expanding and adapting site-scale risk quantification tools and methods to enable assessment of risks and inform management decisions for basin-scale deployment. Increasingly, this work will leverage next-generation approaches for surrogate modelling, fast prediction, and advanced visualization enabled by machine learning and artificial intelligence to promote virtual learning, scenario evaluation, and augment risk-based decision making.

quantitative risk assessment, geologic carbon stor↗

Rapid Electron Transfer Self-Exchange in Conformationally Dynamic Copper Coordination Complexes

Here we report the electron transfer (ET) self-exchange rate constants (k 11 ) for a pair of Cu II/I complexes utilizing dpa R (dpa = dipicolylaniline, R = OMe, SMe) ligands assessed by NMR line-broadening experiments. These ligands afford copper complexes that are conformationally dynamic in one oxidation state. With R = OMe, the Cu I complex is dynamic, while with R= SMe, the Cu II complex is dynamic. Both complexes exhibit unexpectedly large k 11 of 2.48(6) x 10 5 and 2.21(9) × 10 6 M –1 s –1 for [CuCl(dpa OMe )] +/0 and [CuCl(dpa SMe )] +/0 , respectively. Among the fastest reported for molecular copper coordination complexes to date, that of [CuCl(dpa SMe )] +/0 exceeds all others by an order of magnitude and compares only to those observed in type 1 blue copper proteins. The dynamicity of these complexes establish pre-steady-state con-formational equilibria that minimize the inner sphere reorganization energies to 0.71 and 0.62 eV for R = OMe and SMe, respectively. In contrast to the emphasis on rigidity in the formulation of entatic states applied to blue copper proteins, the success of these two systems highlight the relevance of conformational dynamicity in mediating rapid ET.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of Mammalian In Vivo Enhancers Using Mouse Transgenesis and CRISPR Genome Editing [Book Chapter]

Embryonic morphogenesis is strictly dependent on tight spatiotemporal control of developmental gene expression, which is typically achieved through the concerted activity of multiple enhancers driving cell type-specific expression of a target gene. Mammalian genomes are organized in topologically associated domains, providing a preferred environment and framework for interactions between transcriptional enhancers and gene promoters. While epigenomic profiling and three-dimensional chromatin conformation capture have significantly increased the accuracy of identifying enhancers, assessment of subregional enhancer activities via transgenic reporter assays in mice remains the gold standard for assigning enhancer activity in vivo. Once this activity is defined, the ideal method to explore the functional necessity of a transcriptional enhancer and its contribution to target gene dosage and morphological or physiological processes is deletion of the enhancer sequence from the mouse genome. Here we present detailed protocols for efficient introduction of enhancer-reporter transgenes and CRISPR-mediated genomic deletions into the mouse genome, including a step-by-step guide for pronuclear microinjection of fertilized mouse eggs. We provide instructions for the assembly and genomic integration of enhancer-reporter cassettes that have been used for validation of thousands of putative enhancer sequences accessible through the VISTA enhancer browser, including a recently published method for robust site-directed transgenesis at the H11 safe-harbor locus. Together, these methods enable rapid and large-scale assessment of enhancer activities and sequence variants in mice, which is essential to understand mammalian genome function and genetic diseases.

cis-regulatory elements↗

X-ray Emission Spectroscopy of Single Protein Crystals Yields Insights into Heme Enzyme Intermediates

Enzyme reactivity is often enhanced by changes in oxidation state, spin state, and metal-ligand covalency of associated metallocofactors. The development of spectroscopic methods for studying these processes coincidentally with structural rearrangements is essential for elucidating metalloenzyme mechanisms. Herein, we demonstrate the feasibility of collecting X-ray emission spectra of metalloenzyme crystals at a third-generation synchrotron source. In particular, we report the development of a von Hamos spectrometer for the collection of Fe Kβ emission optimized for analysis of dilute biological samples. Here, we further showcase its application in crystals of the immunosuppressive heme-dependent enzyme indoleamine 2,3-dioxygenase. Spectra from protein crystals in different states were compared with relevant reference compounds. Complementary density functional calculations assessing covalency support our spectroscopic analysis and identify active site conformations that correlate to high- and low-spin states. These experiments validate the suitability of an X-ray emission approach for determining spin states of previously uncharacterized metalloenzyme reaction intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intergranular Hotspots: A Molecular Dynamics Study on the Influence of Compressive and Shear Work

Numerous crystal- and microstructural-level mechanisms are at play in the formation of hotspots, which are known to govern high explosives initiation behavior. Most of these mechanisms, including pore collapse, interfacial friction, and shear banding, involve both compressive and shear work done within the material and have thus far remained difficult to separate. Here, we assess hotspots formed at shocked crystal–crystal interfaces using quasi-1D molecular dynamics simulations that isolate effects due to compression and shear. Two high explosive materials are considered (TATB and PETN) that exhibit distinctly different levels of molecular conformational flexibility and crystal packing anisotropy. Temperature and intramolecular strain energy localization in the hotspot are assessed through parametric variation of the crystal orientation and two velocity components that respectively modulate compression and shear work. The resulting hotspots are found to be highly localized to a region within 5–20 nm of the crystal–crystal interface. Compressive work plays a considerably larger role in localizing temperature and intramolecular strain energy for both materials and all crystal orientations considered. Shear induces a moderate increase in energy localization relative to unsheared cases only for relatively weak compressive shock pressures of approximately 10 GPa. These results help isolate and rank the relative importance of hotspot generation mechanisms and are anticipated to guide the treatment of crystal–crystal interfaces in coarse-grained models of polycrystalline high-explosive materials.

36 MATERIALS SCIENCE↗

Responses to International Accrediting Services (IAS) Biennial Onsite Assessment of ALAB to CA ELAP Requirements

The purpose of this assessment was to perform an evaluation of the laboratory’s quality system, capabilities, and personnel qualifications to determine the extent of conformance to the current TNI standards and the rules enacted by the 2020 California Environmental Laboratory Accreditation Program (ELAP) for accreditation of environmental laboratories. The scope of the assessment included the California Code, Health and Safety Code – HSC § 100829 and 100830, the 2016 TNI-2 requirements, published methods, and the laboratory’s Quality Management System including administrative and technical operating procedures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Robust and scalable uncertainty estimation with conformal prediction for machine-learned interatomic potentials

Abstract Uncertainty quantification (UQ) is important to machine learning (ML) force fields to assess the level of confidence during prediction, as ML models are not inherently physical and can therefore yield catastrophically incorrect predictions. Established a-posteriori UQ methods, including ensemble methods, the dropout method, the delta method, and various heuristic distance metrics, have limitations such as being computationally challenging for large models due to model re-training. In addition, the uncertainty estimates are often not rigorously calibrated. In this work, we propose combining the distribution-free UQ method, known as conformal prediction (CP), with the distances in the neural network’s latent space to estimate the uncertainty of energies predicted by neural network force fields. We evaluate this method (CP+latent) along with other UQ methods on two essential aspects, calibration, and sharpness, and find this method to be both calibrated and sharp under the assumption of independent and identically-distributed (i.i.d.) data. We show that the method is relatively insensitive to hyperparameters selected, and test the limitations of the method when the i.i.d. assumption is violated. Finally, we demonstrate that this method can be readily applied to trained neural network force fields with traditional and graph neural network architectures to obtain estimates of uncertainty with low computational costs on a training dataset of 1 million images to showcase its scalability and portability. Incorporating the CP method with latent distances offers a calibrated, sharp and efficient strategy to estimate the uncertainty of neural network force fields. In addition, the CP approach can also function as a promising strategy for calibrating uncertainty estimated by other approaches.

74 ATOMIC AND MOLECULAR PHYSICS↗

Assessment the leaching characteristics and long-term leaching behavior of some radionuclides from synthesized zeolite cement matrix

Highlights: • Synthesis and characterization of zeolite cement synthesized from fly ash • Leaching tests were used to assess the release rate of {sup 85}Sr and {sup 60}Co radionuclides. • Simple mathematical models were used to detect leaching mechanisms. • Long-term leaching behavior of {sup 85}Sr and {sup 60}Co from cementitious matrix was assessed. The development of cementitious materials remains a vital goal to produce valuable products with good mechanical, physical and chemical properties suitable for the safe disposal of concentrated radionuclides resulted from the treatment of contaminated solutions. In this paper, zeolite cement with good properties was laboratory synthesized from industrial by-products fly ash and characterized using various characterization techniques. The leaching characteristics of strontium and cobalt radionuclides from the synthesized zeolite cement were scrutinized conforming with the standard leaching methodology of International Atomic Energy Authority (IAEA). A mechanical strength assessment was executed to characterize the extent of immobilization process of the solidified matrices. The cumulative leaching fraction (φ) of the two studied radionuclides was found to be less than 5% in all examined conditions, which implies the applicability of the IAEA-recommended methodology for estimating the diffusion coefficient. The experimental leaching data were regressed nonlinearly to various mathematical kinetic models to assess the controlling leaching mechanism and to determine the leaching parameters. The regression results indicated that strontium ({sup 85}Sr) and cobalt ({sup 60}Co) leaching resulted from two succeeding mechanisms: as first order kinetic reaction, and then diffusion. The calculated values of leachability indices signify that the performance of each of the studied matrices is within an acceptable range. A simplified mathematical model, rooted in the first order reaction and diffusion mechanisms, was simulated to predict the radionuclides leaching rates from zeolite cement matrices. By comparing the synthesized zeolite cement with other cementitious materials, it can be concluded that the synthesized material can be classified as an efficient material suitable to immobilize {sup 85}Sr and {sup 60}Co from radioactive wastes. The acquired findings demonstrated that the studied immobilized waste matrices have acceptable mechanical effectiveness.

36 MATERIALS SCIENCE↗

Enhanced Light Outcoupling from OLEDs Fabricated on Novel Low-Cost Patterned Plastic Substrates of Varying Periodicity

OLEDs continue to make strides in display applications, but their commercial utilization in solid-state lighting (SSL) is lagging. An ongoing challenge, in particular for manufacturing, is the need for enhanced efficiency and hence the necessity to increase in an inexpensive approach the extraction of the light generated inside the OLED into the forward (viewing) hemisphere. In conventional OLEDs fabricated on a transparent flat anode coated on glass, the external quantum efficiency (EQE) is only ~20%. About 50% of the light is lost to internal waveguiding in the high refractive index (RI) organic + ITO anode layers and to surface plasmon polaritons (SPPs) at the organic/metal cathode interface. Another ~30% of the light is externally waveguided in the substrate to its edges. While extraction of the externally waveguided light is commonly addressed by adding a microlens array (MLA) or a scattering layer at the substrate’s air-side, light outcoupling increases by only ~1.6-1.7x (vs up to 2.5x in improving from ~20% to ~50%). The use of a hemispherical lens or an index matching fluid (IMF) at the substrate/photodetector (PD) interface increases the outcoupling by at least 2x; these approaches however, are not viable industrially, and even a MLA is sometimes undesirable due to its non-planar, scattering structure. In multi-stack tandem OLEDs, where the metal cathode is far from the emitting zone(s), the impact of photons loss to SPPs decreases. Our project addressed the ~50% loss to the internally waveguided light and SPPs. We evaluated OLEDs fabricated on patterned or planarized plastic substrates manufactured in a cost-effective approach compatible with a roll-to-roll (R2R) process. The OLEDs were either (i) patterned to various degrees depending on the pitch a and height or depth h of the pattern features or (ii) planar, with a pattern buried under a flat high RI planarization layer. We demonstrated that the outcoupling from green patterned OLEDs reaches ~50% by mitigating plasmon–related loss and internal waveguiding, even without the addition of a MLA, a hemispherical lens, or IMF. Simulations conducted in parallel with the experimental effort demonstrated how diffraction by conformally corrugated OLEDs increases the outcoupling to >60%. Structures with varying pitch values were also simulated indicating that combining domains of varying pitch could increase outcoupling to 55-60%. Experimentally, we additionally assessed the role a and h in determining not only the OLED efficiencies, but also their structural properties, i.e., the uniformity and conformality throughout the OLED stack. As planar OLEDs are preferred over corrugated devices, we studied different patterns in plastic substrates that were planarized by a high RI formulation. Planar green OLEDs on such structures showed enhanced efficiencies with EQEs larger than 60% with the addition of an IMF (to extract the substrate mode) at the substrate/Si PD interface. White OLEDs showed EQEs of 45.5%. Plastic substrates are currently less attractive than glass substrates due to drawbacks such as permeability to water vapor and oxygen, and in some cases thermal instability. Plastic substrates however, are flexible and easy to handle unlike thin flexible glass, and once transparent thin barrier films are available, they will become more attractive; they are already of interest in medical applications. Importantly, as it is easy to generate various patterns in different plastic materials, they provide excellent means for assessing and optimizing enhancing extracting structures. Such structures can also be transferred to glass substrates with some process modifications. The technical effectiveness and economic feasibility of the project lie in the patterning of the extracting plastic substrates in an approach that is scalable to R2R manufacturing. R2R processes are of drastically lower-cost than batch or single-unit fabrication. The patterned plastic can be a part of an integrated substrate either plastic or glass, which includes also a MLA or a planar layer with embedded scattering particles, as well as a conductive metal mesh/electrode design. SSL is environmentally-friendly and as OLED SSL becomes more efficient it will reduce electricity consumption, and hence lighting cost, as well as produce less expensive attractive lighting fixtures. Our university-industry collaboration is hence of major benefit to the public as it demonstrates the feasibility of manufacturing optimized extracting substrates for highly efficient OLEDs for SSL in a future R2R process, which would drastically reduce the manufacturing cost and increase production in the USA. Moreover, newly developed methods by our team allow low-cost roll manufactured substrates to be transferred to flexible or rigid glass substrates, which solves the plastic substrate barrier issues, and when combined with device encapsulation will increase the OLEDs’ environmental stability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Multi-scale computer-aided design and photo-controlled macromolecular synthesis boosting uranium harvesting from seawater

By integrating multi-scale computational simulation with photo-regulated macromolecular synthesis, this study presents a new paradigm for smart design while customizing polymeric adsorbents for uranium harvesting from seawater. A dissipative particle dynamics (DPD) approach, combined with a molecular dynamics (MD) study, is performed to simulate the conformational dynamics and adsorption process of a model uranium grabber, i.e., PAO m -b-PPEGMA n , suggesting that the maximum adsorption capacity with atomic economy can be achieved with a preferred block ratio of 0.18. The designed polymers are synthesized using the PET-RAFT polymerization in a microfluidic platform, exhibiting a record high adsorption capacity of uranium (11.4 ± 1.2 mg/g) in real seawater within 28 days. This study offers an integrated perspective to quantitatively assess adsorption phenomena of polymers, bridging metal-ligand interactions at the molecular level with their spatial conformations at the mesoscopic level. The established protocol is generally adaptable for target-oriented development of more advanced polymers for broadened applications.

97 MATHEMATICS AND COMPUTING↗