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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 OSTI2025

Cation selectivities in zwitterion grafted nanopores: effect of zwitterion architecture

Selective separation of monovalent cations is a critical challenge in applications such as water purification and lithium recovery from salt brines. Cross-linked zwitterionic amphiphilic copolymer (ZAC-X) membranes have gained attention for their exceptional anion permselectivity, attributed to self-assembled zwitterion-lined nanodomains that interact preferentially with anions according to their hydrated radii r hyd . However, these membranes show minimal selectivity among monovalent cations, despite significant differences in their hydration structures, motivating studies on the underlying mechanisms of cation transport and selectivity in this family of materials. In this study, we conducted molecular dynamics simulations of aqueous salt solutions within zwitterion-functionalized nanopores to elucidate the influence of dipole orientation of the zwitterionic (ZI) ligands on cation diffusivities, partitioning, and permeabilities. To this end, we examined two contrasting ZI ligand architectures: Motif A (surface–cation–anion, S–ZI + –ZI − ) and Motif B (surface–anion–cation, S–ZI − –ZI + ). Our results show that in Motif A, the sulfonate groups of the ZI ligands are localized near the pore center radially, leading to strong electrostatic interactions with small bare cations (Mg 2+ and Li + ). This configuration results in high cation partitioning but low cation diffusion, maintaining solution-diffusion tradeoff typical of functionalized membranes. In contrast, Motif B show that sulfonate groups shift radially toward the mid-region of the pore. This shift, especially for small bare cations, introduces steric constraints that weaken their interactions with the sulfonate groups, thereby enhancing hydration and lowering partitioning, while still maintaining their low self-diffusivity. These findings establish zwitterion dipole orientation as a powerful design lever for tuning cation selectivity in membrane systems and offer molecular-level insights for engineering next-generation ion separation materials.

Morishita, Kazuya [Univ. of Texas, Austin, TX (Uni↗
DOE OSTI2026

Ionic Liquid‐Driven Modulation of DNA Brush Morphology on Nanoparticle Surfaces

Here, the morphology of DNA is strongly influenced by its surrounding environment, including factors such as pH, salt type and valency, and the presence of polymers. Inorganic salts are known to reduce the DNA chain length through mechanisms like electrostatic screening and ion bridging. In contrast, ionic liquids, a new class of organic salts, have previously been found to increase the DNA chain length, indicating a distinct mode of interaction between the ionic liquid and DNA chains. This study utilizes self-assembled DNA-AuNPs as a model system to examine changes in the DNA chain morphology and the nanoscale interaction mechanisms in an ionic liquid environment. The DNA chain lengths are measured in solution using X-ray scattering measurements at varying concentrations of two imidazolium ([$BMIM$] acetate and [$EMIM$] acetate) based ionic liquids. Additionally, Molecular Dynamics (MD) simulations are performed mimicking the experimental system. Our results suggest an interplay of electrostatic and groove-binding interactions governing the DNA chain morphology, which depends on IL concentration and the composition of the DNA chains. It has been found that for DNA chains with majority ssDNA, electrostatic interaction dominate, however with increasing composition of double strands, the DNA chains exhibit compaction due to a non-electrostatic hydrophobic groove-binding mechanism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

From Pollutant Removal to Renewable Energy: MoS2-Enhanced P25-Graphene Photocatalysts for Malathion Degradation and H2 Evolution

The widespread presence of pesticides—especially malathion—in aquatic environments presents a major obstacle to conventional remediation strategies, while the ongoing global energy crisis underscores the urgency of developing renewable energy sources such as hydrogen. In this context, photocatalytic water splitting emerges as a promising approach, though its practical application remains limited by poor charge carrier dynamics and insufficient visible-light utilization. Herein, we report the design and evaluation of a series of TiO2-based ternary nanocomposites comprising commercial P25 TiO2, reduced graphene oxide (rGO), and molybdenum disulfide (MoS2), with MoS2 loadings ranging from 1% to 10% by weight. The photocatalysts were fabricated via a two-step method: hydrothermal integration of rGO into P25 followed by solution-phase self-assembly of exfoliated MoS2 nanosheets. The composites were systematically characterized using X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectroscopy (DRS), and photoluminescence (PL) spectroscopy. Photocatalytic activity was assessed through two key applications: the degradation of malathion (20 mg/L) under simulated solar irradiation and hydrogen evolution from water in the presence of sacrificial agents. Quantification was performed using UV-Vis spectroscopy, gas chromatography–mass spectrometry (GC-MS), and thermal conductivity detection (GC-TCD). Results showed that the integration of rGO significantly enhanced surface area and charge mobility, while MoS2 served as an effective co-catalyst, promoting interfacial charge separation and acting as an active site for hydrogen evolution. Nearly complete malathion degradation (~100%) was achieved within two hours, and hydrogen production reached up to 6000 µmol g−1 h−1 under optimal MoS2 loading. Notably, photocatalytic performance declined with higher MoS2 content due to recombination effects. Overall, this work demonstrates the synergistic enhancement provided by rGO and MoS2 in a stable P25-based system and underscores the viability of such ternary nanocomposites for addressing both environmental remediation and sustainable energy conversion challenges.

Chemistry↗
DOE OSTI2026

Mechanisms of Metal Additive-Induced Ordering During SNIPS Membrane Formation

Isoporous membranes can be fabricated by combining self-assembly with nonsolvent induced phase separation (SNIPS) using an amphiphilic block copolymer like polystyrene-b-poly(4-vinylpyridine) (SV). Poly(4-vinylpyridine) (V) is known to complex with metal salts, which are hypothesized to stabilize solution ordering and preserve structure during casting. We explored how the molar ratio of metal additive to the poly(4-vinylpyridine) block affected the final membrane morphology via scanning electron microscopy (SEM). Dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and in situ grazing-incidence SAXS were used to track changes in solution ordering and chain conformation as a function of the molar ratio of the additive to the V block. Additives induced aggregation, promoted the formation of more compact conformations in solution, and facilitated micelle ordering onto lattices at optimal ratios. Furthermore, these experimental results were supported by random phase approximation calculations, which helped explain how the thermodynamic order–disorder transition shifts with additive binding strength. Stronger additive–polymer interactions reduced the block copolymer volume fraction required for ordering in solution, allowing ordered domains to form at lower polymer concentrations.

Additives↗
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 OSTI2026

Two-Dimensional Perovskite Single-Nanowire Photodetectors

High-performance microphotodetectors require materials that combine strong light–matter interaction, fast charge transport, and ambient stability. Here, we demonstrate single-nanowire devices based on the 2D perovskite (TPA3) 2 PbBr 4 , synthesized via a controlled slow-cooling self-assembly process that yields defect-minimized, anisotropic nanowires with smooth facets. These microphotodetectors exhibit ultralow dark currents (∼10 –15 A), high responsivity (up to 156 mA W –1 ), and exceptional specific detectivity (∼10 11 Jones) under near-UV (405 nm) illumination, with rise and fall times in the millisecond regime. The superior detectivity is primarily driven by the suppression of thermal noise through the material’s ultralow dark current, while the millisecond temporal response is governed by high-intensity trap-filling dynamics. The devices maintain stable operation over 4000 s of continuous on/off cycling and show remarkable ambient stability over weeks, attributed to dense crystal packing and robust organic cation layers. Furthermore, the influence of nanowire thickness on the charge collection efficiency is systematically elucidated through optical penetration depth analysis, highlighting design principles for optimizing low-dimensional perovskite photodetectors. This study introduces single 2D perovskite nanowires as a versatile platform for miniaturized, high-performance optoelectronic devices.

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

Atomic Alignment in PbS Nanocrystal Superlattices with Compact Inorganic Ligands via Reversible Oriented Attachment of Nanocrystals

Nanocrystals (NCs) serve as versatile building blocks for the creation of functional materials with NC self-assembly offering opportunities to enable novel material properties. Here, in this work, we demonstrate that PbS NCs functionalized with strongly negatively charged metal chalcogenide complex (MCC) ligands, such as Sn 2 S 6 4– and AsS 4 3– , can self-assemble into all-inorganic superlattices with both long-range superlattice translational and atomic-lattice orientational order. Structural characterizations reveal that the NCs adopt an unexpected edge-to-edge alignment, and numerical simulation clarifies that orientational order is thermodynamically stabilized by many-body ion correlations originating from the dense electrolyte. Furthermore, we show that the superlattices of Sn 2 S 6 4– -functionalized PbS NCs can be fully disassembled back into the colloidal state, which is highly unusual for orientationally attached superlattices with atomic-lattice alignment. The reversible oriented attachment of NCs, enabling their dynamic assembly and disassembly into effectively single-crystalline superstructures, offers a pathway toward designing reconfigurable materials with adaptive and controllable electronic and optoelectronic properties.

Landau-Ginzburg theory↗
DOE OSTI2025

Mesocrystal growth through oriented sliding and attachment of nanoplates

Oriented attachment is a critical, yet poorly understood, crystal growth pathway based on the self-assembly of nanocrystals. During oriented attachment, solvent-separated particles align and coalesce through forces that enable precise rotation and translation. While prior studies emphasized intragap forces driving crystallographic alignment, the forces enabling uniform stacking and superlattice formation remain unclear. Here, we demonstrate how macroscopic gibbsite mesocrystals emerge from nanoplates guided into staggered positions by directional sliding. Electron microscopy and X-ray scattering reveal the monoclinic superlattice structure, based on nanoplate stacking with a uniform ≈50° stagger along the gibbsite [010] direction. In situ liquid-cell TEM captures preferential sliding along the gibbsite [010] direction, decelerating with increasing particle overlap. Molecular dynamics simulations reveal that this staggered arrangement corresponds to a global free-energy minimum, rather than full alignment. The simulations also confirm that sliding along the [010] direction is energetically favored and provide insight into the role of interfacial water in achieving long-range ordered assemblies. These insights highlight the energy landscape’s role in oriented attachment, with implications for material synthesis and hierarchical structures in nature.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Why are Lead Iodide‐Based Perovskite Precursor Inks Yellow?

A challenge faced by metal halide perovskite (MHP) photovoltaics is scaling up solution deposition processes to realize rapid and inexpensive manufacturing. The challenge lies in completely understanding and controlling solution speciation, nucleation, and self-assembly of iodoplumbate complexes during solvent evaporation as the liquid transforms into gels and solids. An accurate description of solution species, at all points in the transformation, is a prerequisite to design robust and reliable processes. Here, in this study, the common assumption that initial monoplumbate solution species typically invoked (e.g., [PbI 6 ] 4− ) are certainly not the origin of optical absorbance at >400 nm wavelengths is disproved, as are many large particles of common “intermediate” iodoplumbate phases with face- or edge-sharing connectivity. Instead, a new perspective is offered, involving (partially) corner-sharing iodo(poly)plumbates (>1 Pb 2+ per complex) that experience highly dynamic chemical environments. It is outlined how the MHP field would benefit by elucidating these phenomena. Future work is required to determine the size and kinetic behavior of polyplumbate species, and contextualize these findings in relation to broader trends in materials chemistry beyond MHPs. Ultimately, a complete explanation for the solution speciation, optical absorbance signatures, and the color of MHP precursor inks remains an open challenge to the community.

14 SOLAR ENERGY↗
DOE OSTI2025

Lines of Bound States in the Continuum in Monodisperse Microsphere Structures

Incorporating epitaxially grown active semiconductor media into self-assembled microsphere crystals has remained a major challenge as the curved geometry of the spheres is incompatible with conventional planar growth and patterning techniques. As a result, active photonic devices based on such self-assembled structures, which have other desirable properties such as enabling the rapid assembly of large area systems, have been elusive. Here, we numerically demonstrate an alternative route to creating high-Q resonances in microsphere-based nanophotonic assemblies compatible with standard optical gain materials. We show that close-packed layers of monodisperse microspheres can exhibit symmetry bandgaps, regardless of their layer stacking order. Thus, this microsphere environment can be used to create lines of bound states in the continuum (BICs) of an embedded slab made of active material. Using a realistic ZnS@SiO 2 (core-shell) architecture and sphere diameters compatible with scalable colloidal assembly, we predict sharp spectral features in angle-resolved transmission that trace these lines of BICs and persist in the presence of some fabrication disorder. Altogether, in enabling the integration of unpatterned epitaxial gain slabs with large-area colloidal microsphere assemblies, this approach opens a practical path toward active, dynamically reconfigurable photonic devices that leverage BIC physics for narrow-linewidth lasing and enhanced light–matter interactions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Mesoporous Thin Film Architectures: Addressing Material Demands through Molecular Self-Assembly

Mesoporous thin films spark interest across a wide range of disciplines due to their tunable nanostructures, large internal surface areas, and strong compatibility with planar optical, electronic, and microfluidic devices. While attention in the porous materials community has shifted toward macroporous or disordered nanoporous systems, a resurgence in mesoporous thin film research is underway, driven by new molecular self-assembly methods, advanced materials chemistry, and improved characterization techniques. The integration of high-χN block copolymer design, kinetically persistent micelle templating, and postdeposition processing protocols now allows control over structural parameters such as pore size, wall thickness, porosity, and connectivity. These advances have overcome many of the thermodynamic and processing constraints that previously limited widespread adoption. Rather than serving only as high-surface-area supports, mesoporous thin films are engineered as active interfaces where responsive chemistries and nanoscale confinement act in tandem. Embedding switchable ligands, thermoresponsive polymers, redox mediators, or ion-selective groups directly within the pore walls enables real-time control over transport, optical, and electrochemical properties. These capabilities open up new directions in adaptive coatings, gated membranes, and fast-response biosensors. To further expand their functional scope, mesoporous films are integrated into hierarchical and multicomponent architectures. Techniques such as triblock terpolymer templating, crack-directed assembly, and nanoimprint lithography allow for control over spatial organization on the micron and submicron scale and pore system orientation. This enables programmable anisotropy, enhanced molecular diffusion, and wavelength-selective photonic behavior, essential for next-generation sensing, catalysis, and energy applications. Such structural and functional complexity requires equally sophisticated characterization. Multimodal and in situ techniques can track material dynamics under operational conditions. Recent progress includes extended-range ellipsometric porosimetry (EP) for hierarchical architectures, vacuum EP for interface energetics, time-resolved EP for diffusion kinetics, and correlative AFM-SAXS mapping. The introduction of advanced neutron-based spectroscopies, particularly quasielastic neutron scattering (QENS), promises to provide real-time access to ion transport dynamics and segmental motion under nanoscale confinement, offering a path toward deeper mechanistic understanding of structure-performance correlations in mesoporous systems. This Account reflects the technical advances made and the interdisciplinary collaborations that have shaped our collective vision. The particular dimensions of mesopores enable us to subtly tune interactions at the molecular, interfacial, and mesoscopic levels that permit us to harness nanoconfinement. What emerges is a versatile, modular platform capable of chemical gating, energy transduction, and sensing with a level of tunability unmatched by other porous materials. We highlight critical challenges including the need for more robust large-area processing, a deeper understanding of dynamic behavior under cycling, and better integration with device-level architectures. Our strategies support the transition of mesoporous thin films into active high-performance components in next-generation energy, environmental, and biomedical systems.

oxides↗
DOE OSTI2026

Amphiphilic Baskets for Supramolecular Nanoarchitectures at Interfaces: Inverted Monolayer Formation on Water

Interfacial chemistry of molecular baskets remains poorly understood despite their promise for supramolecular applications of detection and sequestration of toxic molecules including those of illicit drugs, organophosphorus compounds, and anticancer agents. We present a fundamental investigation of the interfacial behavior of three amphiphilic supramolecular baskets (ASB 4, 8, and 12), having increasingly longer yet linear alkyl chains at the top of their bowl-shaped cavity. The studies were completed at the air−water interface to elucidate surface activity, interfacial stability, self-assembly, and monolayer organization that drive inverted monolayer formation, in which the molecular arms orient toward the aqueous phase in a configuration opposite to that typically observed for lipids. Herein, surface pressure−area isotherms of ASB 4, 8, 12, deposited on a water surface, were performed in tandem with nonequilibrium relaxation experiments to quantify surface activity, thermodynamic stability, and monolayer compressibility of the baskets’ monolayer assembly. Brewster angle microscopy enabled direct visualization of morphological evolution, aggregation, and packing at the interface. We show that systematic extension of the hydrocarbon arms, from four to 12 methylene groups, progressively modifies intermolecular packing, drives distinct two-dimensional aggregation pathways, and increases number densities at the air−water interface. Atomistic molecular dynamics simulations corroborate many of these experimentally observed trends and provide mechanistic detail on the cooperative roles of basket topology and interfacial concentration in regulating the hydration structure and dynamics within the cavities generated by surface-adsorbing baskets, consistent with observed variations in surface activity and packing. Our results establish how the topology of these unique supramolecules and their concentration govern interfacial organization and offer a rational framework for designing amphiphiles with predictable behavior at soft interfaces.

Hydrocarbons↗
DOE OSTI2025

Self-Assembly of Anisotropic Particles on Curved Surfaces

The surface curvature of membranes, interfaces, and substrates plays a crucial role in shaping the self-assembly of particles adsorbed on these surfaces. However, little is known about the interplay between particle anisotropy and surface curvature and how they couple to alter the free energy landscape of particle assemblies. Using molecular dynamics simulations, we investigate the effect of prescribed curvatures on a quasi-2D assembly of anisotropic patchy particles. By varying curvature and surface coverage, we uncover a rich geometric phase diagram, with curvature inducing ordered structures entirely absent on planar surfaces. Large spatial domains of ordered structures can contain hidden microdomains of orientational textures imprinted by the surface on the assembly. The dynamical landscape is also reshaped by surface curvature, with a glass-like state emerging at modest densities and high curvature. Changes to the symmetry of the surface curvature are found to result in distinct structures, including phases with mesoscale ordering. In conclusion, our findings show that the coupling between surface curvature and particle geometry opens an unexplored space of morphologies and structures that can be exploited for material design.

Fluids↗
DOE OSTI2026

Substrate-Directed Dimensional and Phase Control of Peptide Assemblies on Two-Dimensional van der Waals Materials

Understanding and controlling biomolecular self-assembly on van der Waals (vdW) materials has the potential to advance hybrid bioelectronic devices by enabling precise tuning of the interface and modulation of the resulting electronic properties of the biomolecule-vdW heterostructure. However, how surface properties of vdW materials direct biomolecule assembly remains poorly understood. To fill this knowledge gap, we investigated the assembly of a peptide known to assemble into two-dimensional (2D) crystalline films on MoS 2 on three representative vdW surfaces: WS 2 , MoS 2 , and highly oriented pyrolytic graphite (HOPG). Using in situ atomic force microscopy (AFM), we find that assembly is substrate-dependent, resulting in multilayers on WS 2 , monolayers on MoS 2 , and multiple coexisting phases on HOPG. WS 2 exhibits a higher negative charge, strong long-range electrostatic interactions, and extensive hydration layering that may promote multilayer stacking. In contrast, MoS 2 has stronger short-range interactions with the peptides but much weaker long-range interactions and hydration structure, which may favor monolayer formation. Molecular dynamics simulations predict a corresponding switch from monolayer to multilayer aggregates of the adsorbed monomers, reflected in their relative mobilities. On hydrophobic HOPG, the peptides bind most strongly and remain as monomers with high surface mobility. The peptide dimers comprising the basic unit of the crystals are more compact on HOPG, which has a smaller lattice constant than WS 2 or MoS 2 , suggesting strain contributes to stabilizing multiple phases. Our results provide mechanistic insights into how surface charge and hydration structure, and the lattice structure of the substrates governs peptide assembly on vdW materials, offering a framework to rationally control the 2D peptide-vdW heterostructures.

Molecular dynamics simulations↗
DOE OSTI2026

Polymorphism in Self-Assembly of Short Peptoid Sequences

Due to various applications enabled by diverse morphologies of self-assembled sequence-defined polymers, controlling the self-assembly of synthetic peptidomimetics into designed morphologies has emerged as a promising route for the development of bioinspired functional materials. Herein, we report morphological control over the assembly of a series of short peptoids, or poly-N-substituted glycines, that contain asymmetric hydrophobic domains. We demonstrate that the inherent flexibility of amphiphilic peptoid bilayers drives assembly polymorphism, resulting in the coexistence of nanosheets, twisted ribbons, and nanofibers three distinct morphologies. By tuning peptoid molecular interactions through variations in sequence design, solution pH, and temperature, we demonstrate precise control over the twisting and folding of peptoid bilayers, enabling the formation of well-defined nanosheets and nanohelices. Molecular dynamics simulations further unravel how the introduction of asymmetric hydrophobic domains enables the flexibility of peptoid bilayers and results in peptoid assembly polymorphism. By tuning peptoid molecular interactions through heating, we further demonstrate the transformation of nanosheets into nanohelices. We envision that our mechanistic investigation of peptoid assembly polymorphism provides a strong foundation for leveraging peptoid sequences and chemistries to achieve controlled molecular interactions, driving the creation of biomimetic materials with tailored morphologies and functionalities.

assembly polymorphism↗
DOE OSTI2025

Shape-anisotropy inverses the behavior of emergent vortices in active chiral fluids

Active colloidal fluids exhibit spontaneous emergence of correlated states, characterized by complex collective dynamics and self-organization. In geometrically confined systems, activity modulations trigger robust polar state reversals of a macroscopic vortex formed by colloidal rollers. Here, we reveal that the shape anisotropy of dielectric rollers transforms the system into a chiral active fluid comprised of rollers of arbitrary handedness. The chiral rollers self-assemble into multiple freestanding vortices with a spontaneously selected sense of rotation. We demonstrate that upon reactivation of the system after a complete cessation of activity beyond all relevant timescales, the vortices simultaneously restore their previous chiral states in striking contrast to the chiral state reversals demonstrated by spherical rollers. The analysis reveals that shape-anisotropy modifies the collective state memory of the ensemble. The findings provide insights into the emergence of complex collective behavior in chiral colloidal fluids governed by an interplay between shape anisotropy, chiral motion, and activity modulations.

Colloids↗
DOE OSTI2026

Strong Effect of Nonpolar Solvent Molecular Structure on CdSe Nanoplatelet Stacking

We report a drastic difference in stacking behavior of oleic acid-stabilized 4-monolayer (4 ML) CdSe nanoplatelets (NPLs) in toluene and methylcyclohexane (MCH), two nonpolar solvents that differ in the conformational flexibility of their molecules. Using liquid cell transmission electron microscopy (TEM) and small angle scattering (SAXS) techniques, we show that NPLs form microns-long ribbons consisting of 4 ML CdSe NPLs in toluene, the solvent widely used to form stable colloidal solutions of a broad range of quasi-spherical nanoparticles. In contrast, 4 ML CdSe NPLs are well dispersed in MCH. The difference in stacking behavior of NPLs in toluene and MCH suggests that the conformational flexibility of the solvent molecules, such as the ability to adopt multiple chair conformations, modulates nanoplatelet interactions. Molecular dynamics (MD) simulations reveal that solvent molecules subtly alter the structure of the organic ligand shell. These solvent-dependent changes propagate to the inorganic core, modulating the degree of CdSe nanoplatelet (NPL) twisting and, consequently, the properties of the nanoparticles. We show that toluene better solvates oleate ligands while MCH induces a bimodal oleate span distribution, which can lead to increased solubility of CdSe NPLs. In addition, the solvent can also influence the inorganic core, which, in turn, can modify the nanoparticle properties. We demonstrate that destabilization of toluene solution containing ribbons of 4 ML CdSe NPLs without CdS shells results in the formation of NPL assemblies with amplified spontaneous emission (ASE) with a low threshold of 14 µJ cm−2 that is comparable with that of CdSe/CdS core/shell NPLs. Our results emphasize that the solvent plays a major role in mediating interactions between NPLs and hence their processability for fabrication of functional structures.

CdSe↗