Search NASA⌕ Search

SEARCH · Search NASA

Results for “polymer micelle”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Hydrophobic pockets built in polymer micelles enhance the reactivity of Cu 2+ ions

We report the hydrophobicity-enhanced reactivity of Cu2+ ions as an ester hydrolase. Using a dipicolylamine (DPA) containing reversible addition–fragmentation chain transfer agent, the synthetic sequence, either hydrophobic or hydrophilic first in amphiphilic block copolymers of polystyrene-block-poly(N'N-dimethylacrylamide) (PS-b-PDMA), was varied to control the location of the binding motif, DPA, in the hydrophobic core or on the hydrated corona of polymer micelles. The hydrophobicity of Cu 2+ sites showed a significant impact (as large as 60 times more activity) on their catalytic efficiency towards ester hydrolase. With two different kinetic modes, including Michaelis–Menten and the reverse saturation kinetics models, the binding constant Kb of the substrates to Cu 2+ sites were quantitatively analyzed and we demonstrate that hydrophobicity favors the binding of the substrates to Cu2+ sites at polymer micelles with smaller sizes, however, K b decays exponentially with micellar diameters. Despite the diffusion barrier, hydrophobicity shows a profound impact on the catalytic rate constant kc that measures the single conversion rate of bound substrates to products. There is a 16–20 times kinetic enhancement in the hydrolase activity, completely endowed by the hydrophobic microenvironment of Cu 2+ sites compared to micelles with similar sizes. Our results indicate how the hydrophobicity of Cu 2+ -containing micelles can impact the catalytic efficiency and potentially illustrate a promising way toward the design of bioinspired catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

Lipid-absorbing Polymers

The removal of bile acids and cholesterol by polymeric absorption is discussed in terms of micelle-polymer interaction. The results obtained with a polymer composed of 75 parts PEO and 25 parts PB plus curing ingredients show an absorption of 305 to 309%, based on original polymer weight. Particle size effects on absorption rate are analyzed. It is concluded that crosslinked polyethylene oxide polymers will absorb water, crosslinked polybutadiene polymers will absorb lipids; neither polymer will absorb appreciable amounts of lipids from micellar solutions of lipids in water.

Marsh, H. E., Jr.↗
DOE OSTI2024

Investigating microstructure evolution in block copolymer membranes

Block copolymer self-assembly in conjunction with nonsolvent-induced phase separation (SNIPS) has been increasingly leveraged to fabricate integral-asymmetric membranes. The large number of formulation and processing parameters associated with SNIPS, however, has prevented the reliable construction of high performance membranes. In this study, we apply dynamical self-consistent field theory to model the SNIPS process and investigate the effect of various parameters on the membrane morphology: solvent selectivity, nonsolvent selectivity, initial film composition, and glass transition composition. We examine how solvent selectivity and concentration of polymers in the film impact the structure of micelles that connect to form the membrane matrix. In particular, we find that preserving the order in the surface layer and forming a connection between the supporting and surface layer are nontrivial and sensitive to each parameter studied. Furthermore, the effect of each parameter is discussed, and suggestions are made for successfully fabricating viable block copolymer membranes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

DNA-caged nanoparticles via electrostatic self-assembly

DNA-modified nanoparticles enable DNA sensing and therapeutics in nanomedicine and are also crucial for nanoparticle self-assembly with DNA-based materials. However, methods to conjugate DNA to nanoparticle surfaces are limited, inefficient, and lack control. Inspired by DNA tile nanotechnology, we demonstrate a new approach to nanoparticle modification based on electrostatic attraction between negatively charged DNA tiles and positively charged nanoparticles. This approach does not disrupt nanoparticle surfaces and leverages the programmability of DNA nanotechnology to control DNA presentation. We demonstrated this approach using a variety of nanoparticles, including polymeric micelles, polystyrene beads, gold nanoparticles, and superparamagnetic iron oxide nanoparticles with sizes ranging from 5–20 nm in diameter. DNA cage formation was confirmed through transmission electron microscopy (TEM), neutralization of zeta potential, and a series of fluorescence experiments. DNA cages present “handle” sequences that can be used for reversible target attachment or self-assembly. Handle functionality was verified in solution, at the solid–liquid interface, and inside fixed cells, corresponding to applications in biosensing, DNA microarrays, and erasable immunocytochemistry. Finally, these experiments demonstrate the versatility of the electrostatic DNA caging approach and provide a new pathway to nanoparticle modification with DNA that will empower further applications of these materials in medicine and materials science.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Concentration-Driven Slowdown of Chain-Exchange Kinetics in Block Copolymer Micelle Solutions

Here, we investigate the dependence of chain-exchange kinetics on polymer concentration for spherical micelles prepared from a polystyrene-b-poly(ethylene-alt-propylene) (SEP) diblock copolymer ( M n = 75 kDa, Ð = 1.05, and f PS = 0.18) in the PEP-selective solvent squalane. Solutions with concentrations of 15 vol% or more adopt a body-centered-cubic (BCC) packing of micelles, or a dense liquid-like packing (LLP), as confirmed by small-angle X-ray scattering. Concurrently, the mean aggregation number of the micelles grows steadily from about 60 in dilute solution to nearly 200 by 50 vol%. Time-resolved small-angle neutron scattering (TR-SANS) analysis reveals a monotonic and substantial (i.e., more than four orders of magnitude) decrease in the rate of chain exchange as the polymer concentration increases from 1 to 50 vol%. The TR-SANS relaxation functions are analyzed, taking into account both changes in contrast (due to chain exchange) and evolution in the structure factor (due to refinement of micelle packing). The activation energy for chain pullout is extracted using an established model and can be expressed as a linear function of polymer concentration, indicating that, in addition to the enthalpic barrier for extracting the core block, the evolution of micelle characteristics with increasing concentration imposes further constraints on chain exchange. Consistent with a theory of Halperin, these results suggest that the dominant factor reflects steric penalties during core block pullout arising from a reduced interfacial area per chain and associated increased corona crowding, due to the increase in aggregation number. The rate of exchange is independent of whether the micelles adopt a BCC or LLP arrangement, confirming that the rate-limiting step is extraction of the core block.

chemical structure↗
DOE OSTI2025

Bayesian inference of anisotropic 2D small-angle scattering from sparse measurement

Here, we present a Bayesian inference framework for reconstructing anisotropic two-dimensional small-angle scattering (2D SAS) patterns from sparse, noisy, or partially missing data. The method combines a symmetry-aware angular basis with radial Gaussian process priors to enable accurate, training-free interpolation and denoising. Computational benchmarks demonstrate reliable recovery of both isotropic and high-order anisotropic features under severe data reduction. Experimental validations on stretched polymers, sheared wormlike micelles, and carbon fibers show improved fidelity and resolution compared to raw measurements, achieving comparable accuracy with up to 50-fold fewer detected neutrons. This approach enables quantitative structural analysis under low-flux, time-limited, or single-shot conditions, extending the applicability of 2D SAS techniques to compact neutron sources and mechanically driven soft matter systems undergoing transient structural changes.

Tung, Chi-Huan [Oak Ridge National Laboratory (ORN↗
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 OSTI2023

Effect of Charged Block Length Mismatch on Double Diblock Polyelectrolyte Complex Micelle Cores

Polyelectrolyte complex micelles are hydrophilic nanoparticles that self-assemble in aqueous environments due to associative microphase separation between oppositely charged blocky polyelectrolytes. In this work, we employ a suite of physical characterization tools to examine the effect of charged block length mismatch on the equilibrium structure of double diblock polyelectrolyte complex micelles (D-PCMs) by mixing a diverse library of peptide and synthetic charged-neutral block polyelectrolytes with a wide range of charged block lengths (25–200 units) and chemistries. Early work on D-PCMs suggested that this class of micelles can only be formed from blocky polyelectrolytes with identical charged block lengths, a phenomenon referred to as chain length recognition. Here, we use salt annealing to create PCMs at equilibrium, which shows that chain length recognition, a longstanding hurdle to repeatable self-assembly from mismatched polyelectrolytes, can be overcome. Interestingly, D-PCM structure–property relationships display a range of values that vary systematically with the charged block lengths and chemical identity of constituent polyelectrolyte pairings and cannot be described by generalizable scaling laws. We discuss the interdependent growth behavior of the radius, ionic pair aggregation number, and density in the micelle core for three chemically distinct diblock pairings and suggest a potential physical mechanism that leads to this unique behavior. By comparing the results of these D-PCMs to the scaling laws recently developed for single diblock polyelectrolyte complex micelles (S-PCMs: diblock + homopolymer), we observe that D-PCM design schemes reduce the size and aggregation number and restrict their growth to a function of charged block length relative to S-PCMs. Understanding these favorable attributes enables more predictive use of a wider array of charged molecular building blocks to anticipate and control macroscopic properties of micelles spanning countless storage and delivery applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Breast tumor-targeted drug delivery via polymer nanocarriers: Endogenous and exogenous strategies

Breast cancer, one of the most common types of cancer worldwide, has a high degree of malignancy while lacking efficient treatments. The off-target events frequently occurring in drug administration have been a major obstacle, which causes severe side effects to patients and reduces the therapeutic efficacy. An ideal medication should precisely target the specific site with precise control over concentration and duration. In recent years, there has been immense progress in polymer nanocarriers that demonstrate great potential in the targeted delivery. These nanocarriers are constructed from materials sensitive to a wide range of endogenous (e.g., pH, enzyme, redox) and exogenous stimuli (e.g., light, ultrasound, magnetic waves), driving cargo release to the targeted tissue or cells. Here, we elucidate the mechanism of current targeting strategies and the engineering methods to construct these targeting systems or to improve their targeting efficiency. Here we capture the recent progress in the targeted nanocarriers derived from polymers which span hydrogels and micelles, demonstrating their design and applications in chemo, hyperthermia, immuno, and gene therapies.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Upper critical solution temperature polymer assemblies via variable temperature liquid phase transmission electron microscopy and liquid resonant soft X-ray scattering

Abstract Here, we study the upper critical solution temperature triggered phase transition of thermally responsive poly(ethylene glycol)- block -poly(ethylene glycol) methyl ether acrylate- co -poly(ethylene glycol) phenyl ether acrylate- block -polystyrene nanoassemblies in isopropanol. To gain mechanistic insight into the organic solution-phase dynamics of the upper critical solution temperature polymer, we leverage variable temperature liquid-cell transmission electron microscopy correlated with variable temperature liquid resonant soft X-ray scattering. Heating above the upper critical solution temperature triggers a reduction in particle size and a morphological transition from a spherical core shell particle with a complex, multiphase core to a micelle with a uniform core and Gaussian polymer chains attached to the surface. These correlated solution phase methods, coupled with mass spectral validation and modeling, provide unique insight into these thermoresponsive materials. Moreover, we detail a generalizable workflow for studying complex, solution-phase nanomaterials via correlative methods.

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

Minimal implicit-solvent coarse-grained simulation of Pluronic block copolymers with ionic liquids

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 ([C n C 1 im]) and 1‐alkyl‐3‐methylpyrrolidinium ([C n C 1 pyrr]), 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. Furthermore, 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.

Atomistic simulations↗
DOE OSTI2024

Self-assembled complex micelle phase stability in ABA-type triblock copolymers and related core-shell bottlebrushes

We report the synthesis and temperature-dependent morphologies of a series of polylactide--poly (-decalactone)--polylactide (LDL) triblock copolymers with M n = 16.0 – 18.1 kg / mol and volume fractions f L = 0.27 – 0.31 and associated core-shell bottlebrush (csBB) polymers, which derive from enchaining LDL triblocks through a polymerizable midchain functionality. While the LDL triblocks form micellar Frank-Kasper A15 and phases due to the conformational asymmetry of this monomer pair, the csBB morphologies sensitively depend on the backbone degree of polymerization ( N bb ). At low N bb values, micellar Frank-Kasper phases with the brush backbone situated in the matrix domain are stable, albeit with a modest reduction in the mean interfacial curvature evidenced by a to A15 order-to-order transition. However, larger N bb values drive csBBs to form hexagonally packed cylinders phases. This N bb -dependent phase behavior is rationalized in terms of a star-to-bottlebrush transition. At low N bb values, the csBBs are akin to star polymers with pointlike junctions that can support complex micelle packings. As N bb increases, the csBBs adopt cylindrical molecular geometries with extended backbones situated in the matrix domain that prefer hexagonally packed cylinders morphologies. Published by the American Physical Society 2024

Materials Science↗
DOE OSTI2024

Engineering a biopolymer for vascular embolization based on fundamental polymer principals

Herein we describe the engineering of a potential polymer substitute to metal coils for achieving vascular embolization. Our system is based on a methacrylate end-functionalized polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) triblock copolymer which displays thermal-reversible gelation properties and FCC ordering of the original copolymer while also being able to chemically crosslink. This system shows injectability, two-step gelation, chemical crosslinking with a five-fold increase in modulus and is highly resistant to washout under physiological flow conditions. Furthermore, we show that exposure to aqueous flow imparts resistance to swelling where less than 10 % swelling was observed under physiological flow as opposed to more than 60 % under static conditions after 30 days. Auxiliary experiments with PEO-PPO-PEO copolymers of various molecular weights indicate that this phenomenon may possibly be attributed to entanglements known to occur between adjacent micelles, where the reptation time, the time for polymer disentanglement, is long compared to the flow rate.

36 MATERIALS SCIENCE↗
NASA NTRS1991

Hexagonal and nematic phases of chains. I - Correlation functions. II - Phase transitions

The statistical mechanics of a system of semiflexible chains, which can represent polymer liquid crystals, long-chain biomolecules, stiff wormlike micelles, or columns of discotic liquid crystals, are examined. A continuum theory is used to calculate static correlation functions in the hexagonal and nematic phases. Two correlation functions are considered: (1) the structure factor which describes fluctuations in the density; and (2) the director fluctuation spectrum, which describes fluctuations in the local optical axis. In addition, a model is developed for the phase transitions of a system of infinitely long, semiflexible chains which interact through a steric, excluded-volume repulsion. The model yields generic phase diagrams in terms of pressure or density vs. persistence length or temperature.

Selinger, Jonathan V.↗
NASA NTRS1992

Flow-induced gelation of living (micellar) polymers

The effect of shear velocity gradients on the size (L) of rodlike micelles in dilute and semidilute solution is considered. A kinetic equation is introduced for the time-dependent concentration of aggregates of length L, consisting of 'bimolecular' combination processes L + L-prime yield (L + L-prime) and unimolecular fragmentations L yield L + (L - L-prime). The former are described by a generalization (from spheres to rods) of the Smoluchowski mechanism for shear-induced coalesence of emulsions, and the latter by incorporating the tension-deformation effects due to flow. Steady-state solutions to the kinetic equation are obtained, with the corresponding mean micellar size evaluated as a function of the Peclet number P (i.e., the dimensionless ratio of the flow rate and the rotational diffusion coefficient). For sufficiently dilute solutions, only a weak dependence of the micellar size on P is found. In the semidilute regime, however, an apparent divergence in the micellar size at P of about 1 suggests a flow-induced first-order gelation phenomenon.

Bruinsma, Robijn↗
DOE OSTI2025

How Does the Rate of Chain Exchange Relate to Stress Relaxation in Triblock Copolymer Networks?

The relationship between macroscopic stress relaxation and molecular-level chain exchange in triblock copolymer micelles has been explored using rheology and time-resolved small-angle neutron scattering (TR-SANS), marking the first measurements of chain exchange in concentrated triblock networks. It has long been assumed in models of transient or thermoreversible networks that the time scales for these two processes are equal. Experimentally, we find that stress relaxation occurs many orders-of-magnitude faster than chain exchange. This difference is quantitatively explained by modest dispersity in the core block that results in a slight asymmetry within any given nominally symmetric triblock. For stress relaxation to occur, only the shorter chain must pull out, while chain exchange is slowed due to the requirement of the eventual pullout of the longer block. The pullout time is extremely sensitive to the length of the core block. This mechanism is supported by measurements with an intentionally asymmetric triblock copolymer, which displays an even larger difference between the stress relaxation and chain exchange rates. These results establish a quantitative molecular-level picture of the chain dynamics associated with stress relaxation in triblock copolymer networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗