The ethylene oxide (EO)/propylene oxide (PO) triblock copolymers (EO)m-(PO)n-(EO)m, also known as poloxamers, self-assemble in aqueous solution due to the differences in hydrophobicity between EO and PO. Both the overall length of the blocks and their relative lengths in the copolymer impact self-assembly. Even though poloxamers lack charge, they respond to the presence of salts, including ionic liquids (ILs). Here, the response of poloxamer 188 to 1-alkyl-3-methylimidazolium chlorides having long and short alkyl chains was studied by small-angle neutron scattering. The dilute state of both the polymer and ILs was studied, with the IL concentrations being below published critical micelle concentrations. The goal was to probe initial stages of self-assembly. The results demonstrate a clear interaction between the long chain imidazolium chloride and the poloxamer that is surfactant-like, which is not observed for the short alkyl chain salt.

Pluronic block copolymers, composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) in a triblock structure (PEO-PPO-PEO), are well known for their amphiphilic character and ability to self-assemble into micelles in aqueous solution. The addition of ionic liquids (ILs) can further modulate the core-shell structures of these copolymers, influencing their stability, critical micellization temperature, and size. However, fully atomistic simulations often become prohibitively expensive due to the size and complexity of these systems. In this work, coarse-grained simulations using a minimal implicit-solvent model were performed to examine how two classes of ILs, namely, 1-alkyl-3-methylimidazolium ([CnC1im]) and 1-alkyl-3-methylpyrrolidinium ([CnC1pyrr]), change the micellization of Pluronic block copolymers in aqueous solution. The effects of IL concentration and alkyl group length were investigated, and the model greatly improved the efficiency of simulating large-scale micelle systems. The numerical simulations are qualitatively compared with experimental investigations. Our results show that adding ILs expands the micelle core by embedding IL tails among the PPO blocks, thereby increasing overall micelle size. Less polar ILs generally induce more pronounced micellar growth. However, the effect of IL tail length on conformation and micellar packing is non-monotonic. Up to moderate chain lengths (around C8-C10), the IL tails can extend sufficiently to increase local separation within the micelle; at longer tail lengths, enhanced hydrophobic clustering and steric hindrance cause the tails to bend or fold, capping further expansion. In addition, although block copolymer chains tend to pack more closely in the presence of longer-tailed ILs, the random coil size of an individual polymer chain does not necessarily shrink. Meanwhile, these insights provide a deeper understanding of how Pluronic/IL systems interact, informing applications in drug delivery, cosmetics, food, and environmental engineering. Finally, our minimal implicit-solvent model can be applied to larger systems and longer timescales, substantially reducing computational cost while reproducing key structural trends observed experimentally.

Controlling the orientation of nanostructured block copolymer (BCP) thin films is essential for their use in templating, transport, and pattern transfer. Conventional efforts mainly focus on adjusting enthalpic interactions between the blocks and interfaces, while entropic contributions are often overlooked. Here, we show that the morphology of BCP thin films can be precisely tuned by the architectural design of star BCPs. Specifically, we synthesized multiarm star BCPs with a polystyrene (PS) core and poly(2-vinylpyridine) (P2VP) corona, which exhibits a lamellar microdomain morphology. The entropic penalty associated with a parallel orientation of the microdomains to the substrate is controlled by varying the number of arms comprising the star BCPs, from 2-arms (triblock) to 3-arms and 4-arms. We systematically investigated the thin film morphology at different depths using grazing incidence small-angle X-ray and neutron scattering (GISAXS and GISANS), atomic force microscopy (AFM), water contact angle (WCA), and interference microscopy. The results show that 2-arm star BCPs show a parallel orientation, the 3-arm star BCPs form a uniform PS film at the air surface with a vertical orientation of the microdomains underneath, and the 4-arm star BCPs exhibit a parallel microdomain orientation at the air surface with mixed parallel and perpendicular microdomain orientation in the bulk. Additionally, we found that the inclination angle of microdomains at the edges of islands and holes, resulting from the incommensurability between film thickness and the characteristic period of the microdomain morphology, increases with a higher number of arms. This suggests a greater grain boundary tilt angle in the microdomains of star-shaped block copolymers (BCPs). When silicon substrates were modified with PS homopolymer, the selective interaction between substrate and core blocks promotes a parallel orientation for the 4-arm star BCPs. This work shows that control of arm number in star BCPs affords diverse BCP thin film morphologies, offering insights into the star BCP conformations in thin films across different depths.

Proteins can perform ideal therapeutic functions. However, their large size and significant surface hydrophilicity and charge prohibit them from reaching intracellular targets. These chemical features also render them poorly encapsulated by nanoparticles used for intracellular delivery. In this work, a novel combination of protein vesicles and hydrophobic ion pairing (HIP) was used to load protein cargo and achieve cytosolic delivery to overcome the limitations of previous protein vesicle properties. Protein vesicles are thermally self-assembling nanoparticles made from elastin-like polypeptide (ELP) fused to an arginine-rich leucine zipper and a globular protein fused to a glutamate-rich leucine zipper. To impart stimuli-responsive disassembly, physiological stability, and small size, the ELP sequence was modified to include histidine and tyrosine residues. HIP was used to load and release protein cargo requiring endosomal escape for cytosolic function. HIP vesicles enabled delivery of cytochrome c, a cytosolically active protein, and a significant reduction in viability in both a traditional two-dimensional (2D) human cancer cell line culture and a biomimetic three-dimensional (3D) organoid model of acute myeloid leukemia. By examining the uptake of positively and negatively charged fluorescent protein cargos loaded by HIP, this work revealed the necessity of HIP for cytosolic cargo delivery and how HIP loading influences protein vesicle self-assembly and disassembly using microscopy, small-angle X-ray scattering, and nanoparticle tracking analysis. HIP protein vesicles have the potential to broaden the use of intracellular proteins as therapeutics for various diseases and extend protein vesicles to deliver other biomacromolecules, as the strategy developed here resulted in the first cytosolic protein cargo delivery using protein vesicles.

Recently, a solvent segregation driven gel (SeedGel) has been demonstrated to be a tunable and versatile way to stabilize bicontinuous structures in a binary solvent. Here, the structure properties of the SeedGel prepared with two miscible solvents, 3-methylpyridine (3MP)/water and deuterated 3MP (d-3MP)/water, are systematically investigated using ultra-small angle neutron scattering (USANS), small angle X-ray and neutron scattering (SAXS and SANS). The structures of samples prepared with 3MP/water show similar behavior to one previous SeedGel prepared with lutidine/water. Interestingly, the deuteration of 3MP significantly shifts the gelation temperature of the SeedGel. The results also demonstrate that both components of the binary solvent can be exchanged between the formed two domains of a SeedGel when changing the temperature. Importantly, the binary solvent used for the SeedGel preparation does not have to undergo bulk phase transition as a function of temperature. Our results show that the correlation length due to the density fluctuation of the binary solvent is about the same at the gelation transition temperature for all studied SeedGels prepared with different binary solvents. Thus, this correlation length seems to be a key controlling parameter for SeedGel formation. It is noted that this observation not only holds in binary solvents that show a bulk phase separation but also exists in miscible binary solvents without bulk phase separation. The results here thus open a window to prepare SeedGels with a new set of binary solvents that may have been overlooked before and provide guidance for choosing appropriate miscible binary solvents that can be used to prepare SeedGels.

The HIV-1 fusion peptide, which is a short hydrophobic peptide from the gp41 coat glycoprotein that participates in the infection of a cell, interacts with model lipid bilayer membranes in a concentration-dependent manner. The interaction of the peptide with the bilayer also strongly depends on the lipid composition. Here, molecular dynamics simulations were performed to investigate lipid-specific interactions that arise shortly after the binding of a less-fusogenic variant of the HIV-1 fusion peptide to a lipid bilayer composed of a mixture of dimyristoyl phosphatidylcholine and dimyristoyl phosphatidylglycerol. The impact of peptide concentration was also studied. An improved understanding was gained of the lipid-specific interactions experienced by the FP. New insight was also gained into how the peptide concentration changes these interactions.

A strategy is outlined for quantitatively evaluating the particle density profiles from small-angle scattering spectra of dilute solutions. The approach employs an orthonormal basis function expansion method, enabling the determination of characteristic mass distributions in self-assembled structures without the need for a specific structural model. Through computational benchmarking, the efficacy of this approach is validated by effectively reconstructing the density profile of soft-ball systems with varying fuzziness from their scattering signatures. The feasibility of the method is demonstrated by fitting small-angle neutron scattering data obtained from Pluronic L64 micelles at different temperatures. This proposed approach is both simple and analytical, eliminating the requirement for a presumptive structural model in scattering analysis. The new method could therefore facilitate quantitative descriptions of complex nanoscopic structures inherent to numerous soft-matter systems using small-angle scattering techniques.

NPM1 is an abundant nucleolar chaperone that, in addition to facilitating ribosome biogenesis, contributes to nucleolar stress responses and tumor suppression through its regulation of the p14 Alternative Reading Frame tumor suppressor protein (p14ARF). Oncogenic stress induces p14ARF to inhibit MDM2, stabilize p53 and arrest the cell cycle. Under non-stress conditions, NPM1 stabilizes p14ARF in nucleoli, preventing its degradation and blocking p53 activation. However, the mechanisms underlying the regulation of p14ARF by NPM1 are unclear because the structural features of the p14ARF-NPM1 complex remain elusive. Here we show that NPM1 sequesters p14ARF within phase-separated condensates, facilitating the assembly of p14ARF into a gel-like meso-scale network. This assembly is mediated by intermolecular contacts formed by hydrophobic residues in an α-helix and β-strands within a partially folded N-terminal domain of p14ARF. Those hydrophobic interactions promote phase separation with NPM1, enhance nucleolar partitioning of p14ARF, restrict p14ARF and NPM1 diffusion within condensates and in nucleoli, and reduce cell viability. Our structural model provides novel insights into the multifaceted chaperone function of NPM1 in nucleoli by mechanistically linking the nucleolar localization of p14ARF to its partial folding and meso-scale assembly upon phase separation with NPM1.

Solid-supported amines having low molecular weight branched poly(ethylenimine) (PEI) physically impregnated into porous solid supports are promising adsorbents for CO2 capture. Co-impregnating short-chain poly(ethylene glycol) (PEG) together with PEI alters the performance of the adsorbent, delivering improved amine efficiency (AE, mol CO2 sorbed/mol N) and faster CO2 uptake rates. To uncover the physical basis for this improved gas capture performance, we probe the distribution and mobility of the polymers in the pores via small angle neutron scattering (SANS), solid-state NMR, and molecular dynamic (MD) simulation studies. SANS and MD simulations reveal that PEG displaces wall-bound PEI, making amines more accessible for CO2 sorption. Solid-state NMR and MD simulation suggest intercalation of PEG into PEI domains, separating PEI domains and reducing amine-amine interactions, providing potential PEG-rich and amine-poor interfacial domains that bind CO2 weakly via physisorption while providing facile pathways for CO2 diffusion. Contrary to a prior literature hypothesis, no evidence is obtained for PEG facilitating PEI mobility in solid supports. Instead, the data suggest that PEG chains coordinate to PEI, forming larger bodies with reduced mobility compared to PEI alone. We also demonstrate promising CO2 uptake and desorption kinetics at varied temperatures, facilitated by favorable amine distribution.

Solid-supported amines are effective CO2 adsorbents capable of capturing CO2 from flue gas streams (10-15 vol % CO2) and from ultradilute streams, such as ambient air (similar to 400 ppm CO2). Amine sorbents have demonstrated promising performance (e.g., high CO2 uptake and uptake rates) with stable characteristics under repeated, idealized thermal swing conditions, enabling multicycle application. Literature studies suggest that solid-supported amines such as PEI/SBA-15 generally exhibit slowly reducing CO2 uptake rates or capacities over repeated thermal swing capture-regeneration cycles under simulated DAC conditions. While there are experimental reports describing changes in supported amine mass, degradation of amine sites, and changes in support structures over cycling, there is limited knowledge about the structure and mobility of the amine domains in the support pores over extended use. Furthermore, little is known about the effects of H2O on cyclic applications of PEI/SBA-15 despite the inevitable presence of H2O in ambient air. Here, we present a series of neutron scattering studies exploring the distribution and mobility of PEI in mesoporous silica SBA-15 as a function of thermal cycling and cyclic conditions. Small-angle neutron scattering (SANS) and quasielastic neutron scattering (QENS) are used to study the amine and H2O distributions and amine mobility, respectively. Applying repeated thermal swings under dry conditions leads to the thorough removal of water from the sorbent, causing thinner and more rigid wall-coating PEI layers that eventually lead to slower CO2 uptake rates. On the other hand, wet cyclic conditions led to the sorption of atmospheric water at the wall-PEI interfaces. When PEI remains hydrated, the amine distribution (i.e., wall-coating PEI layer thickness) is retained over cycling, while lubrication effects of water yield improved PEI mobility, in turn leading to faster CO2 uptake rates.

We used grazing-incidence small-angle neutron scattering (GISANS) to probe the depth-dependent orientation of self-assembled morphologies of block copolymers. A hydrophobic???hydrophobic block copolymer, poly(solketal methacrylate)-block-polystyrene (PSM-b-PS), was synthesized and spin-coated into films tens of nanometers in thickness where the polymers adopted a disordered state. PSM-b-PS was then hydrolyzed by exposing the polymer thin film to trifluoroacetic acid vapor or embedding a photoacid generator in the film during spin coating, followed by exposure to UV light. The hydrolysis converted the block copolymer into a hydrophilic???hydrophobic block copolymer, poly(glycerol monomethacrylate)-block-polystyrene (PGM-b-PS), significantly increasing the segmental interaction parameter (??) and causing microphase separation of the copolymers. GISANS was used to study the depth-dependent structure of the films and revealed that the orientation of the microphase-separated structure differed at the polymer???air and polymer???substrate interfaces. In the regions where the lamellae were parallel to the interfaces, the orientation propagated into the film from the interfaces. However, in the areas where the lamellae were perpendicular to the interfaces, the orientation did not persist with increasing distance from the interfaces.

Block copolymer (BCP) structure and dynamics were studied using small-angle neutron scattering (SANS), neutron spin echo (NSE) spectroscopy, and molecular dynamics (MD) simulations to obtain a fundamental understanding of the impact of an interfacial block on chain dynamics. A glassy block acted as the interface, and the dynamics of a rubbery block was studied. The rubbery block was protonated near the interface in one sample and near the chain end in another sample to observe the interfacial effect on the rubbery polymer. Analysis of the structure and dynamics revealed that the interfacial rubbery block was confined in layered morphologies and exhibited much slower dynamics than the chain-end rubbery block that was dispersed in the rubbery matrix. The interfacial rubbery block showed weaker dynamical relaxation than that at the chain end, and it also had critically important length scale dependence. Dynamical slowing was only observed at length scales significantly larger than the characteristic segmental length, and the disparity between interfacial and chain-end dynamics increased with increasing length.

The properties of single-component phospholipid lipid bilayers have been extensively characterized. Natural cell membranes are not so simple, consisting of a diverse mixture of lipids and proteins. While having detailed structural information on complex membranes would be useful for understanding their structure and function, experimentally characterizing such membranes at a level of detail applied to model phospholipid bilayers is challenging. Here, small-angle neutron scattering with selective deuteration was used to characterize a binary lipid mixture composed of 1,2-dimyristoyl-3-sn-glycero-phosphatidylcholine and 1,2-dimyristoyl-3-sn-glycero-phosphatidylethanolamine. The data analysis provided the area per lipid in each leaflet as well as the asymmetry of the composition of the inner and outer leaflets of the bilayer. The results provide new insight into the structure of the lipid bilayer when this lipid mixture is used to prepare vesicles.

Nanomaterials must be systematically designed to be technologically viable 1 – 5 . Driven by optimizing intermolecular interactions, current designs are too rigid to plug in new chemical functionalities and cannot mitigate condition differences during integration 6 , 7 . Despite extensive optimization of building blocks and treatments, accessing nanostructures with the required feature sizes and chemistries is difficult. Programming their growth across the nano-to-macro hierarchy also remains challenging, if not impossible 8 – 13 . To address these limitations, we should shift to entropy-driven assemblies to gain design flexibility, as seen in high-entropy alloys, and program nanomaterial growth to kinetically match target feature sizes to the mobility of the system during processing 14 – 17 . Here, following a micro-then-nano growth sequence in ternary composite blends composed of block-copolymer-based supramolecules, small molecules and nanoparticles, we successfully fabricate high-performance barrier materials composed of more than 200 stacked nanosheets (125 nm sheet thickness) with a defect density less than 0.056 µm −2 and about 98% efficiency in controlling the defect type. Contrary to common perception, polymer-chain entanglements are advantageous to realize long-range order, accelerate the fabrication process (<30 min) and satisfy specific requirements to advance multilayered film technology 3 , 4 , 18 . This study showcases the feasibility, necessity and unlimited opportunities to transform laboratory nanoscience into nanotechnology through systems engineering of self-assembly.

transition temperature shifts (TTS) at high fluence ( t) to at least 1020 n/cm2 (>1 MeV) pertinent to plant operation of some pressurized water reactors (PWR) for 80 full power years. Correlations between the high flux test reactor results and low flux surveillance specimens must be established for proper RPV embrittlement predictions of the current nuclear power fleet. Additionally, a complete understanding of defect evolution for high nickel RPV steels is needed to characterize the embrittlement potential of Mn-Ni-enriched precipitates (MNPs), particularly for the high fluence regime. While understanding of copper-enriched precipitates (CRPs) have been fully developed, the recent discovery and experimental verification [4] of late blooming MNPs with little to no copper for nucleation has stimulated research efforts to understand the evolution of these phases. New and existing databases will be combined to support developing physically based models of TTS for high fluence-low flux ( < 10 11n/cm2-s) conditions, beyond the existing surveillance database, to neutron fluences of at least 1 1020 n/cm2 (>1 MeV). Moreover, large number of various RPV materials have been irradiated in ATR-2 experiment and will be jointly studied by University of California Santa Barbara (UCSB) and ORNL to address majority of microstructural characteristics discussed above, see Ref. [5] and [6] for details. UCSB has performed a large number of SANS experiments in the past at the National Institute of Standards and Technology (NIST) Center for Neutron Research (NCNR). These data are taken from RPV steels irradiated in a wide range of flux-fluence space and will be very useful in comparing to the upcoming UCSB ATR-2 irradiation characterization since most of the SANS experiments with ATR-2 materials will be performed at ORNL High Flux Isotope Reactor (HFIR). However in the previous report [7], some discrepancies were observed between HFIR and NCNR generated data. One of the hypotheses was that there was some kind of extra scattering occurring off the sample holders that results in the HFIR curves falling above the NCNR curves. To test this hypothesis, UCSB provided thermally aged samples that have been previously run at NCNR to ORNL for testing at HFIR while ORNL performed some improvements to experimental set up at HFIR. This report provides the status for the Level 3 Milestone (M3LW-15OR0402013), Complete report detailing comparative analysis of results from High Flux Isotope Reactor and National Institute of Standards and Technology small-angle neutron scattering experiments. This milestone is associated with small-angle neutron scattering characterization at the High Flux Isotope Reactor of various model alloys that had been previously characterized at NCNR by UCSB.

The interaction of many peptides with lipid bilayer membranes strongly depends on the lipid composition. Here, a study of the impact of unsaturated lipid acyl chains on the interaction of a derivative of the HIV-1 fusion peptide with lipid bilayer vesicles is presented. Lipid bilayer vesicles composed of mixtures of lipids with two saturated acyl chains and lipids and one saturated and one unsaturated acyl chain, but identical head groups, were studied. The dependence of the peptide conformation on the unsaturated lipid content was probed by circular dichroism spectroscopy, while the impact of the peptide on the bilayer structure was determined by small-angle neutron scattering. The impact of the peptide on the lipid bilayer vesicle dynamics was investigated using neutron spin echo spectroscopy. Molecular dynamics simulations were used to characterize the behavior of the systems studied to determine if there were clear differences in their physical properties. The results reveal that the peptide–bilayer interaction is not a simple function of the unsaturated lipid acyl chain content of the bilayer. Instead, the peptide behavior is more consistent with that seen for the bilayer containing only unsaturated lipids, which is supported by lipid-specific interactions revealed by the simulations.

Polyelectrolyte complexation plays an important role in materials science and biology. The internal structure of the resultant polyelectrolyte complex (PEC) phase dictates properties such as physical state, response to external stimuli, and dynamics. Small-angle scattering experiments with X-rays and neutrons have revealed structural similarities between PECs and semidilute solutions of neutral polymers, where the total scattering function exhibits an Ornstein-Zernike form. In spite of consensus among different theoretical predictions, the existence of positional correlations between polyanion and polycation charges has not been confirmed experimentally. Here, we present small-angle neutron scattering profiles where the polycation scattering length density is matched to that of the solvent to extract positional correlations among anionic monomers. The polyanion scattering functions exhibit a peak at the inverse polymer screening radius of Coulomb interactions, q^*≈ 0.2 Å^-1. This peak, attributed to Coulomb repulsions between the fragments of polyanions and their attractions to polycations, is even more pronounced in the calculated charge scattering function that quantifies positional correlations of all polymer charges within the PEC. Screening of electrostatic interactions by adding salt leads to the gradual disappearance of this correlation peak, and the scattering functions regain an Ornstein-Zernike form. Experimental scattering results are consistent with those calculated from the random phase approximation, a scaling analysis, and molecular simulations.

Chiral metal–organic frameworks (MOFs) have gained rising attention as ordered nanoporous materials for enantiomer separations, chiral catalysis, and sensing. Among those, chiral MOFs are generally obtained through complex synthetic routes by using a limited choice of reactive chiral organic precursors as the primary linkers or auxiliary ligands. Here, we report a template-controlled synthesis of chiral MOFs from achiral precursors grown on chiral nematic cellulose-derived nanostructured bio-templates. We demonstrate that chiral MOFs, specifically, zeolitic imidazolate framework (ZIF), unc -[Zn(2-MeIm) 2 , 2-MeIm=2-methylimidazole], can be grown from regular precursors within nanoporous organized chiral nematic nanocelluloses via directed assembly on twisted bundles of cellulose nanocrystals. The template-grown chiral ZIF possesses tetragonal crystal structure with chiral space group of P 4 1 , which is different from traditional cubic crystal structure of I -43  m for freely grown conventional ZIF-8. The uniaxially compressed dimensions of the unit cell of templated ZIF and crystalline dimensions are signatures of this structure. We observe that the templated chiral ZIF can facilitate the enantiotropic sensing. It shows enantioselective recognition and chiral sensing abilities with a low limit of detection of 39 μM and the corresponding limit of chiral detection of 300 μM for representative chiral amino acid, D- and L- alanine.

The adsorption of nonionic surfactants onto hydrophilic nanoparticles (NPs) is anticipated to increase their stability in aqueous medium. While nonionic surfactants show salinity- and temperature-dependent bulk phase behavior in water, the effects of these two solvent parameters on surfactant adsorption and self-assembly onto NPs are poorly understood. In this study, we combine adsorption isotherms, dispersion transmittance, and small-angle neutron scattering (SANS) to investigate the effects of salinity and temperature on the adsorption of pentaethylene glycol monododecyl ether (C12E5) surfactant on silica NPs. We find an increase in the amount of surfactant adsorbed onto the NPs with increasing temperature and salinity. Based on SANS measurements and corresponding analysis using computational reverse-engineering analysis of scattering experiments (CREASE), we show that the increase in salinity and temperature results in the aggregation of silica NPs. We further demonstrate the non-monotonic changes in viscosity for the C12E5-silica NP mixture with increasing temperature and salinity and correlate the observations to the aggregated state of NPs. The study provides a fundamental understanding of the configuration and phase transition of the surfactant-coated NPs and presents a strategy to manipulate the viscosity of such dispersion using temperature as a stimulus.

Star block copolymers (s-BCPs), comprised of multiple linear diblock copolymers joined at a central point, are shown to segregate to the interface between two immiscible homopolymers that are identical to the blocks of the s-BCPs. The s-BCPs undergo a configurational transition at the interface, with different blocks of copolymers being embedded in their respective homopolymers, thereby bridging the interface and promoting adhesion. A series of 4-arm s-BCPs were synthesized with hydrogenated or deuterated polystyrene (PS/dPS) as the core block and poly-(2-vinylpyridine) (P2VP) as the corona block, which was directly placed at the interface between the two homopolymers. Neutron reflectivity (NR) was used to determine the concentration profiles of the PS homopolymer, s-BCP core blocks, and P2VP total segments under equilibrium. The investigation varies the molecular weight (MW) and the total number of s-BCPs at the interface. Self-consistent-field theory (SCFT) was also employed to calculate the concentration profiles of the components at the interface, which were in excellent agreement with experimental results. The NR showed that the interfacial width between the homopolymers increased with the increasing number of s-BCPs at the interface up to a saturation limit. Beyond this limit, additional s-BCPs were released into the corona-miscible phase as unimolecular micelles. For a comparable interlayer thickness of s-BCPs at the interface, lower MW s-BCPs generated a broader interface. SCFT analysis suggested that, at the same packing density, the arms of the low MW s-BCPs align more parallel to the interface, while the arms of high MW s-BCPs adopt a more normal orientation, like their linear BCP counterparts. Furthermore, it was also observed that the core blocks, constrained by the junction points, were oriented more parallel and closer to the interface than the corona blocks. The phase behavior of the polymer blends revealed that s-BCP additives can efficiently reduce the domain size, with the low MW yielding smaller domain sizes due to the greater reduction in the interfacial energy and the high MW arresting phase separation due to their higher binding energy and a jamming of the interfacial assemblies. Asymmetric double cantilever beam (ADCB) tests demonstrated that s-BCPs promoted adhesion more efficiently than their linear BCP counterparts due to stronger binding energy per molecule, suggesting a more efficient compatibilizer for polymer upcycling. The results from these studies provide fundamental insights into the assembly of s-BCPs at homopolymer interfaces, the reduction of domain size, and promotion of adhesion, providing a strategy for the use of s-BCPs as stealth surfactants and universal compatibilizers.