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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Structure of Complex Liquid–Liquid Extraction Organic Phases for Rare Earth Separations

Complex, multicomponent liquids with hierarchical structure and phase transitions are encountered in many natural and industrial processes, including in chemical separations. One notable example is aggregation and organic phase splitting in liquid–liquid extraction (LLE) of metal ions. While these two phenomena that have long been closely associated, a mechanistic link between mesoscale structure and the capacity-limiting organic phase splitting remains elusive due to complexity of these systems. Here, in this study, we combine small-angle X-ray scattering (SAXS), X-ray photon correlation spectroscopy (XPCS), and molecular dynamics simulation to reveal a comprehensive picture of structure at the nano- and mesoscale in these complex solutions. For the representative case of rare earth extraction from an acidic aqueous phase by a malonamide extractant in dodecane, we investigate a wide range of process-relevant extractant and acid concentrations to provide a complete picture of how aggregation depends on composition. We decompose organic phase structure from SAXS into two contributions, which together can capture the scattering at all compositions: composition fluctuations described by the Ornstein–Zernike equation at low wavenumber Q, and nanostructure modeled by a “pre-peak” at intermediate Q. The former contains information about the thermodynamics of demixing, while the latter reflects nanoscopic self-assembly of the extractant and extracted solutes. While fluctuations have typically not been considered in the literature, we find they in fact dominate the total structure for nearly all practical conditions. As only the fluctuations have a strong temperature response, we confirm this attribution with temperature-dependent SAXS measurements, including for extracted europium nitrate complexes. SAXS and XPCS measurements near the critical point find static and dynamic scaling consistent with theory. Overall, this new paradigm for understanding LLE organic phases connects composition, nanoscale, and mesoscale structuring to phase behavior, providing both a comprehensive picture of solution structure and a quantitative link between aggregation and third phase formation.

Peroutka, Allison A. [Argonne National Laboratory ↗
DOE OSTI2024

A Versatile Approach to Stabilize Liquid–Liquid Interfaces using Surfactant Self-Assembly

Stabilizing liquid–liquid interfaces, whether between miscible or immiscible liquids, is crucial for a wide range of applications, including energy storage, microreactors, and biomimetic structures. Here, in this study, a versatile approach for stabilizing the water-oil interface is presented using the morphological transitions that occur during the self-assembly of anionic, cationic, and nonionic surfactants mixed with fatty acid oils. The morphological transitions underlying this approach are characterized and extensively studied through small-angle X-ray scattering (SAXS), rheometry, and microscopy techniques. Dissipative particle dynamics (DPD) as a simulation tool is adopted to investigate these morphological transitions both in the equilibrium ternary system as well as in the dynamic condition of the water-oil interface. Such a versatile strategy holds promise for enhancing applications such as liquid-in-liquid 3D printing. Moreover, it has the potential to revolutionize a wide range of fields where stabilizing liquid–liquid interfaces not only offers unprecedented opportunities for fine-tuning nanostructural morphologies but also imparts interesting practical features to the resulting liquid shapes. These features include perfusion capabilities, self-healing, and porosity, which could have significant implications for various industries.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A versatile approach to stabilize liquid-liquid interfaces using surfactant self-assembly

Stabilizing liquid–liquid interfaces, whether between miscible or immiscible liquids, is crucial for a wide range of applications, including energy storage, microreactors, and biomimetic structures. In this study, a versatile approach for stabilizing the water-oil interface is presented using the morphological transitions that occur during the self-assembly of anionic, cationic, and nonionic surfactants mixed with fatty acid oils. The morphological transitions underlying this approach are characterized and extensively studied through small-angle X-ray scattering (SAXS), rheometry, and microscopy techniques. Dissipative particle dynamics (DPD) as a simulation tool is adopted to investigate these morphological transitions both in the equilibrium ternary system as well as in the dynamic condition of the water-oil interface. Such a versatile strategy holds promise for enhancing applications such as liquid-in-liquid 3D printing. Moreover, it has the potential to revolutionize a wide range of fields where stabilizing liquid–liquid interfaces not only offers unprecedented opportunities for fine-tuning nanostructural morphologies but also imparts interesting practical features to the resulting liquid shapes. These features include perfusion capabilities, self-healing, and porosity, which could have significant implications for various industries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Quantitative SANS and multi-model analysis of spacer-dependent micellization of urea-based gemini surfactants

The micellization behavior of urea-based cationic gemini surfactants was investigated using small-angle neutron scattering (SANS) with multi-model form factor analysis. A homologous series of surfactants with urea group included in the hydrophobic tail and polymethylene spacers consisting of two to ten methylene units was analyzed using three form factor models: a core–shell ellipsoid and two variants of homogeneous ellipsoids. The results from all models show a consistent trend of the micelle structures, confirming that the spacer length critically influences micellar geometry, aggregation number, and hydration. The surfactant with four CH 2 groups in the spacer formed the largest micelles with the highest aggregation number, while longer spacers led to progressively smaller, more compact aggregates. The shell hydration—quantified as the volume fraction of heavy water within the hydrophilic region—decreased systematically with increasing spacer length due to enhanced hydrophobicity of the headgroup-spacer region. Intermicellar interactions, modeled as screened Coulomb interaction using the rescaled mean spherical approximation (RMSA), revealed the strongest electrostatic repulsion for the case of four methylene groups in the spacer, corresponding to the highest micellar charge and largest interparticle spacing. The observed spacer-dependent trends were robust across all modeling approaches, demonstrating that the spacer length serves as a key structural determinant of self-assembly in this type of urea-based gemini systems. These findings provide insight into the design of gemini surfactants with tailored aggregation behavior for applications in drug delivery, nanostructure templating, and solubilization technologies.

Core–shell ellipsoid model↗
DOE OSTI2025

Discovery of unconventional and nonintuitive self-assembling peptide materials using experiment-driven machine learning

Prediction of peptide secondary structure is challenging because of complex molecular interactions, sequence-specific behavior, and environmental factors. Traditional design strategies, based on hydrophobicity and structural propensity, can be biased and could indeed prevent discovery of interesting, diverse, and unconventional peptides with desired nanostructure assembly. Using β sheet formation in pentapeptides as a case study, we used an integrated high-throughput experimental workflow and an artificial intelligence–driven active learning framework to improve prediction accuracy of self-assembly. By focusing on sequences where machine learning (ML) predictions deviate from conventional design strategies, we synthesized and tested 268 pentapeptides, successfully finding 96 forming β sheet assemblies, including unconventional sequences (e.g., ILFSM, LMISI, MITIY, MISIW, and WKIYI) not predicted by traditional methods. Our ML models outperformed conventional β sheet propensity tables, revealing useful chemical design rules. A web interface is provided to facilitate community access to these models. This work highlights the value of ML-driven approaches in overcoming the limitations of current peptide design strategies.

Talluri, Y. Nissi [Indian Inst. of Technology (IIT↗
DOE OSTI2024

Access to Advanced Functional Materials through Postmodification of Biomimetic Assemblies via Click Chemistry

The design, synthesis, and fabrication of functional nanomaterials with specific properties remain a long-standing goal for many scientific fields. The self-assembly of sequence-defined biomimetic synthetic polymers presents a fundamental strategy to explore the chemical space beyond biological systems to create advanced nanomaterials. Moreover, subsequent chemical modification of existing nanostructures is a unique approach for accessing increasingly complex nanostructures and introducing functionalities. Of these modifications, covalent conjugation chemistries, such as the click reactions, have been the cornerstone for chemists and materials scientists. Herein, we highlight some recent advances that have successfully employed click chemistries for the postmodification of assembled one-dimensional (1D) and two-dimensional (2D) nanostructures to achieve applications in molecular recognition, mineralization, and optoelectronics. Specifically, biomimetic nanomaterials assembled from sequence-defined macromolecules such as peptides and peptoids are described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Self-Sorting vs Coassembly in Peptide Amphiphile Supramolecular Nanostructures

The functionality of supramolecular nanostructures can be expanded if systems containing multiple components are designed to either self-sort or mix into coassemblies. This is critical to gain the ability to craft self-assembling materials that integrate functions, and our understanding of this process is in its early stages. Here, in this work, we have utilized three different peptide amphiphiles with the capacity to form β-sheets within supramolecular nanostructures and found binary systems that self-sort and others that form coassemblies. This was measured using atomic force microscopy to reveal the nanoscale morphology of assemblies and confocal laser scanning microscopy to determine the distribution of fluorescently labeled monomers. We discovered that PA assemblies with opposite supramolecular chirality self-sorted into chemically distinct nanostructures. In contrast, the PA molecules that formed a mixture of right-handed, left-handed, and flat nanostructures on their own were able to coassemble with the other PA molecules. We attribute this phenomenon to the energy barrier associated with changing the handedness of a β-sheet twist in a coassembly of two different PA molecules. This observation could be useful for designing biomolecular nanostructures with dual bioactivity or interpenetrating networks of PA supramolecular assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Synthetic Band Structure Engineering of Graphene Using Block Copolymer-Templated Dielectric Superlattices

Engineering the electronic band structure of two-dimensional (2D) materials by imposing spatially periodic superlattice (SL) potentials opens a pathway to unconventional electronics. Nanopatterning the gate electrode or surface dielectric near 2D crystals provides a powerful strategy for realizing electrostatically tunable “remote” SLs with flexibility in lattice design. Here, we demonstrate the effectiveness of block copolymer (BCP)-templated dielectric nanopatterns for fabricating etch-free high-grade metal oxide SLs. Alumina (AlO x ) nanopatterns with hexagonal symmetry and a 38 nm SL wavelength are produced as a model material by directly converting a self-assembled BCP film via block-selective vapor phase infiltration. Despite micrometer-scale rotational disorder inherent to BCP self-assembly, electronic transport measurements of graphene reveal replica Dirac points at zero field and Hofstadter mini-gaps under finite magnetic fields. These results indicate the successful formation of remote SL potentials in graphene resulting from optimized AlO x nanopattern fabrication to achieve consistent lattice symmetry and periodicity at a macroscopic scale. The findings of this study, combined with the versatile, scalable, and cost-effective nature of BCP nanopatterning, highlight the potential of BCP-templated nanostructures for remote SL engineering in 2D crystals.

36 MATERIALS SCIENCE↗
DOE OSTI2024

4D-STEM Mapping of Nanocrystal Reaction Dynamics and Heterogeneity in a Graphene Liquid Cell

Chemical reaction kinetics at the nanoscale are intertwined with heterogeneity in structure and composition. However, mapping such heterogeneity in a liquid environment is extremely challenging. Here, in this work, we integrate graphene liquid cell (GLC) transmission electron microscopy and four-dimensional scanning transmission electron microscopy to image the etching dynamics of gold nanorods in the reaction media. Critical to our experiment is the small liquid thickness in a GLC that allows the collection of high-quality electron diffraction patterns at low dose conditions. Machine learning-based data-mining of the diffraction patterns maps the three-dimensional nanocrystal orientation, groups spatial domains of various species in the GLC, and identifies newly generated nanocrystallites during reaction, offering a comprehensive understanding on the reaction mechanism inside a nanoenvironment. This work opens opportunities in probing the interplay of structural properties such as phase and strain with solution-phase reaction dynamics, which is important for applications in catalysis, energy storage, and self-assembly.

four-dimensional scanning transmission electron mi↗
DOE OSTI2025

Reversible Physical Gelation of Thermotropic Liquid Crystals Driven by Nanoplate Self-Assembly

Physically gelled soft materials, driven by the self-assembly of low-molecular-mass gelators (LMGs), have emerged as a platform for designing advanced gels that exhibit reversible gelation and property tunability. Liquid crystal (LC) gels are of great interest due to their supramolecular orderings as gel hosts and their enhanced electro-optical properties. In this study, we demonstrate the physical gelation of a nematic LC driven by nanoplate self-assembly, expanding the concept of gelators from small molecules to nanoparticles. These nanoplates are functionalized with promesogenic ligands and form a fibrillar network in LCs with face-to-face interplate stacking, resembling LMGs. The critical gelation volume fraction in the tilt test is only 0.14 v %, comparable to values reported for LMGs. Rheological analyses confirm viscoelastic properties characteristic of gelation. In situ small-angle X-ray scattering (SAXS) characterizes the formation of nanoplate networks in the LC with decreasing temperature, wherein LC mesogens become trapped in pores. Molecular dynamics (MD) simulations reveal that the interaction between ligand-coated nanoplates and LC-forming mesogens induces a multidomain LC structure, increasing friction between LC domains and stabilizing the gel. This study establishes direct relationships among molecular interactions, nanostructures, and mechanical properties in physically gelled LCs. In conclusion, the findings inspire the future gelator design of both LMGs and nanoplates, with potential applicability in bioscaffold engineering and liquid crystalline nanocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Evaporation of a Reactive Nanofluid Sessile Drop: Capturing Rapid Emergence of Surface Crystals with In Situ Synchrotron X-ray Diffraction

Mechanisms for surface pattern formation from evaporation of a reactive nanofluid sessile drop are not well understood. In contrast to the coffee-ring effect from inert particles, rapid chemical and morphological transformation of reactive nanoparticles upon rapid evaporative drying are challenging to probe experimentally. Here, using grazing-incidence X-ray surface scattering, the nanostructure of nascent surface patterns has been probed as a ZnO nanofluid sessile drop rapidly dries. The high temporal resolution enabled by the high flux of synchrotron X-rays allows the observation of the emergence of Zn(OH) 2 surface crystals from the onset of evaporation and their rapid evolution into the final residual surface pattern, via transient layered complexes evident from the temporary appearance of X-ray diffraction peaks preceding Zn(OH) 2 formation. The results offer mechanistic insights of morphogenesis of surface patterns from evaporation-induced self-assembly and self-organization of reactive nanofluids, previously untenable using other experimental methods.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Spectral Performance of Multilayer Amorphous Selenium and Selenium–Tellurium Photodetectors

The ability to robustly and with scalability detect single photons in the visible spectrum with wavelength resolution would transform many imaging applications. Theoretical studies propose an array of carbon nanotubes (CNTs) functionalized with semiconductor quantum dots (QDs) as a physical realization of such photon sensors. In this work, we report approaches to synthesize these CNT-QD nanostructures using DNA as a smart glue to connect CNTs to QDs.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Formation of tunable diamond micro- and nanopillars for field effect enhancement applications

Here, we developed a process for the fabrication of tunable single crystal diamond micro- and nanopillars, with tip widths ranging from 40 to 460 nm, densities ranging from 0.5 to 53.5 pillars/μm 2 , and heights greater than 4.5 μm. A self-assembled Au nanodot ensemble etch mask was formed from an annealed Au thin film. The nanodot diameter and density can be tuned using the initial film thickness. The pillars were etched from the nanodot mask using an RIE O 2 plasma, which has infinite selectivity for the diamond when applied at low RF powers (50 W). Finally, the pillars can be sharpened to ~40 nm tip widths by annealing in air at 650 °C. These pillars can be used for applications such as field effect enhancement of diamond photocathode devices, enhancement of optical emission from N-V centers, and antireflective coatings.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mapping in situ the assembly and dynamics in aqueous supramolecular polymers

Supramolecular polymers, bonded through directional non-covalent interactions, closely mimic dynamic behaviors of biological nanofibers. However, the complexity of assembly pathways makes it highly challenging to unravel the nature of supramolecular dynamics in aqueous environments. Here we introduce a precise combinatorial titration methodology to probe in situ the assembly of peptide amphiphiles (PAs). This approach reveals a binary assembly mechanism governed by equilibrium between spheroidal micelles and β-sheet polymers. Weakening hydrogen bonding shifts the equilibrium towards micelles and decreases the internal structural order of filamentous polymers, promoting supramolecular dynamics. Extending this methodology to two-component copolymerization systems, we find a surprising tendency to form blocky nanostructures with reduced internal phase separation as the mismatch in peptide sequence decreases. Interestingly, while well-mixed copolymers acquire different dynamics, mismatched ones retain the characteristic supramolecular motion of their homopolymer counterparts. These critical insights into supramolecular dynamics offer strategies to tailor the dynamic functions of supramolecular nanomaterials.

Molecular self-assembly↗
DOE OSTI2024

Unveiling Structural Heterogeneity and Imbalance of Gold Decahedral Nanoparticles using Four-dimensional Scanning Transmission Electron Microscopy

Multi-twinned structures have been observed in technologically important crystal systems, for example diamond cubic and face-centered cubic (FCC) lattices, that include materials such as diamond, silicon, a wide range of noble metals, and their nanoscale counterparts. Beyond atomic building blocks, the special arrangements also occur in the self-assembly of nanoparticles (NP) and μm-sized colloidal particles and occupy parts of their phase diagrams. Spanning a wide range of length scales, the universality of the structures arises when the systems attempt to achieve multitwinned structures by overcoming geometric misfits during minimizing surface energies with entirely {111} or close-packing facets. While it is fundamental to understand how strain is sustained upon twinned structures and symmetry breaking, the knowledge will be paramount in practical aspects such as guiding and controlling the thin film growth, anisotropic NP growth, and self-assembly of NPs. Au decahedral (Dh) NP, as the most prevalent multi-twinned model system, fits five tetrahedral motifs into a circle by sharing an axis resulting in a geometric misfit angle of 7.35°, or a disclination with power of -7.35°. Postulating how Au FCC lattice adopts the misfit, theoretical models have been developed to address the underlying lattice symmetry and inhomogeneous strain distribution separately. Yet, experimental reports regarding the former have been limited due to the relatively large X-ray beam sizes that do not fit the sizes of NPs. On the other hand, though the latter has been widely adapted in the thermodynamics of small (<10 nm) multi-twinned nanoparticles, previous literature has shown that, at edge length of 17 nm, the theory’s is invalidated by shear strain that is observed in a defect-free Au Dh NP by high-resolution transmission electron microscopy (HR-TEM) imaging. Though the advancement of aberrationcorrected scanning transmission electron microscopy (AC-STEM) imaging and ab initio calculation techniques brings new opportunities, along with challenges in complicated image analysis and limitation in particle size (usually below 10 nm), the gap between nanoscale and mesoscale has never been extended to gain insight from atomic system with straightforward interaction potentials.

4D-STEM↗
DOE OSTI2026

Self‐Limiting Polymerization‐Induced Crystallization‐Driven Self‐Assembly (SL‐PI‐CDSA) Enables Templated Synthesis of Chiral Plasmonic, Hybrid 2D Hexagonal Assemblies

Examples of self-regulating synthetic self-assembly are relatively few, with most known chemical systems relying on kinetic rather than thermodynamic control. Herein, we demonstrate the rapid generation (t ≤ 5 min) of size-tunable ultralow dispersity (Ð ≤ 1.01) 2D hexagonal nanosheets governed by self-limiting self-assembly (SLSA). Self-assembly in natural systems occurs with exquisite control of structure, function, and dimension. We demonstrate that key aspects of biological assembly can be rationally applied toward the development of bottom-up approaches for the construction of chiral nanomaterials. To this end, self-limiting polymerization-induced crystallization-driven self-assembly (SL-PI-CDSA) of modular and templating aryl isocyanide (AIC) monomers yields functional 2D assemblies permitting post-polymerization/assembly modifications. Detailed study of the internal and external structure of the hexagonal nanosheets reveals topological defects which offer mechanistic insights into both their assembly and subsequent utilization. Specifically, these features enable fabrication of chiral hybrid organic–inorganic nanomaterials incorporating chiral plasmonic metal nanoparticles (MNPs). Our results suggest that the synergistic interplay of template-driven confinement and hierarchical chirality induce symmetry breaking of in situ-generated gold MNPs. We anticipate that the platform presented will facilitate fabrication of new hybrid, chiral organic–inorganic nanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Mechanism of DNA origami folding elucidated by mesoscopic simulations

Abstract Many experimental and computational efforts have sought to understand DNA origami folding, but the time and length scales of this process pose significant challenges. Here, we present a mesoscopic model that uses a switchable force field to capture the behavior of single- and double-stranded DNA motifs and transitions between them, allowing us to simulate the folding of DNA origami up to several kilobases in size. Brownian dynamics simulations of small structures reveal a hierarchical folding process involving zipping into a partially folded precursor followed by crystallization into the final structure. We elucidate the effects of various design choices on folding order and kinetics. Larger structures are found to exhibit heterogeneous staple incorporation kinetics and frequent trapping in metastable states, as opposed to more accessible structures which exhibit first-order kinetics and virtually defect-free folding. This model opens an avenue to better understand and design DNA nanostructures for improved yield and folding performance.

77 NANOSCIENCE AND NANOTECHNOLOGY↗