Structure Property Relationship of Micellar Waterborne Poly(Urethane-Urea): Tunable Mechanical Properties and Controlled Release Profiles with Amphiphilic Triblock Copolymers.

Waterborne polyurethane (WPU) has attracted significant interest as a promising alternative to solvent-based polyurethane (SPU) due to its positive impact on safety and sustainability. However, significant limitations of WPU, such as its weaker mechanical strength, limit its ability to replace SPU. Triblock amphiphilic diols are promising materials to enhance the performance of WPU due to their well-defined hydrophobic-hydrophilic structures. Yet, our understanding of the relationship between the hydrophobic-hydrophilic arrangements of triblock amphiphilic diols and the physical properties of WPU remains limited. In this study, we show that by controlling the micellar structure of WPU in aqueous solution via the introduction of triblock amphiphilic diols, the postcuring efficiency and the resulting mechanical strength of WPU can be significantly enhanced. Small-angle neutron scattering confirmed the microstructure and spatial distribution of hydrophilic and hydrophobic segments in the engineered WPU micelles. In addition, we show that the control of the WPU micellar structure through triblock amphiphilic diols renders WPU attractive in the applications of controlled release, such as drug delivery. Here, curcumin was used as a model hydrophobic drug, and the drug release behavior from WPU-micellar-based drug delivery systems was characterized. It was found that curcumin-loaded WPU drug delivery systems were highly biocompatible and exhibited antibacterial properties in vitro. Furthermore, the sustained release profile of the drug was found to be dependent on the structure of the triblock amphiphilic diols, suggesting the possibility of controlling the drug release profile via the selection of triblock amphiphilic diols. This work shows that by shedding light on the structure-property relationship of triblock amphiphilic diol-containing WPU micelles, we may enhance the applicability of WPU systems and move closer to realizing their promising potential in real-life applications.

An alternative analysis of contrast-variation neutron scattering data of casein micelles in semi-deuterated milk.

Contrast-variation small-angle neutron scattering (CV-SANS) is an excellent way to determine the structure of complex, hierarchical colloids, including self-assembled biological systems. In these experiments, the scattering length density of solvents is changed (by varying the ratio of water or [Formula: see text] and heavy water or [Formula: see text]) to highlight or mask scattering from different components in the system. This approach has been used with synthetic colloids, but it is also increasingly being used in the biological and food sciences. Perhaps the most studied food colloid is the "casein micelle," a self-assembled nanometer-scale colloid of the structure-forming casein protein in milk. CV-SANS data available in the literature are typically analyzed using approximations, which may be invalid for casein micelles, as they have been shown to be sticky spheres. To assess the applicability of this approximate approach, a comprehensive set of CV-SANS data from casein micelles in diluted milk was reanalyzed using a model-based approach, where the casein micelles were formally treated as interacting spheres. In general, the conclusions of the previous study are reproduced, but this new approach makes it more straightforward to distinguish the different components in milk and can be applied to any dairy sample with known form of interparticle interactions, which offers the possibility of studying semi-deuterated milk at its native concentration.

A Neutron Scattering Study of the Structure of Poly(dimethylsiloxane)-Stabilized Poly(methyl methacrylate) (PDMS-PMMA) Latexes in Dodecane.

Hard-sphere particles in nonpolar solvents are an essential tool for colloid scientists. Sterically stabilized poly(methyl methacrylate) (PMMA) particles have long been used as the exemplary hard-sphere system. However, neither the particles themselves nor the poly(12-hydroxystearic acid) (PHSA) stabilizer necessary to prevent aggregation in nonpolar solvents are commercially available. To counter this, several alternatives have been proposed. In recent years, there has been an increased interest in poly(dimethylsiloxane) (PDMS) stabilizers as a commercially available alternative to PHSA, yet the structure of particles made in this way is not as well understood as those produced using PHSA. In this work, we employ small-angle neutron scattering to determine the internal structure of PDMS-stabilized PMMA particles, synthesized with and without an additional crosslinking agent. We report data consistent with a homogeneous PMMA core with a linearly decaying PDMS shell. The thickness of the shell was in excess of 50 nm, thicker than the PHSA layer typically used to stabilize PMMA but consistent with reports of the layer thickness for similar molecular weight PDMS at planar surfaces. We also show that the amount of the hydrogenous material in the particle core of the crosslinked particles notably exceeds the amount of added ethylene glycol dimethacrylate crosslinker, suggesting some entrapment of the PDMS stabilizer in the PMMA matrix.

Casein micelles in milk as sticky spheres.

Milk is a ubiquitous foodstuff and food ingredient, and milk caseins are key to the structural properties of milk during processing and storage. Caseins self-assemble into nanometer-sized colloids, referred to as "micelles", and particles of this size are ideally suited to study by small-angle scattering (SAS). Previous SAS measurements have almost exclusively focussed on the internal structure of the micelles. While important for milk's properties, this attention to the interior of the micelles provides limited information about the structure-forming properties of milk and milk ingredients. The ultra-small-angle X-ray scattering (USAXS) measurements and analysis in this study extend to the micrometer scale, which makes it possible to characterize the interaction between the micelles. Until now, SAS studies have generally excluded a consideration of the interparticle interactions between casein micelles. This is inconsistent with these new data, and it is not possible to model the data without some interparticle attraction. If the micelles are treated as sticky spheres, excellent agreement between experimental data and model fits can be obtained over the length scales studied, from micrometers to ångströms. The stickiness of casein micelles will impact ultra-small-angle scattering and small-angle scattering measurements of casein micelles, but it particularly limits the application of simple approximations, which generally assume that particles are dilute and noninteracting. In summary, this analysis provides an approach to modelling scattering data over many orders of magnitude, which will provide better understanding of interactions between caseins and during food processing.

Time-resolved small-angle neutron scattering studies of the thermally-induced exchange of copolymer chains between spherical diblock copolymer nanoparticles prepared via polymerization-induced self-assembly.

Sterically-stabilized diblock copolymer nanoparticles (a.k.a. micelles) are prepared directly in non-polar media via polymerization-induced self-assembly (PISA). More specifically, a poly(lauryl methacrylate) chain transfer agent is chain-extended via reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of methyl methacrylate (MMA) to form sterically-stabilized spheres at 20% w/w solids in n-dodecane at 90 °C. Both fully hydrogenous (PLMA39-PMMA55 and PLMA39-PMMA94) and core-deuterated (PLMA39-d8PMMA57 and PLMA39-d8PMMA96) spherical nanoparticles with mean core diameters of approximately 20 nm were prepared using this protocol. After diluting each dispersion in turn to 1.0% w/w with n-dodecane, small-angle X-ray scattering studies confirmed essentially no change in spherical nanoparticle diameter after thermal annealing at 150 °C. Time-resolved small angle neutron scattering was used to examine whether copolymer chain exchange occurs between such nanoparticles at elevated temperatures. Copolymer chain exchange for a binary mixture of PLMA39-PMMA55 and PLMA39-d8PMMA57 nanoparticles produced hybrid (mixed) cores containing both PMMA55 and d8PMMA57 blocks within 3 min at 150 °C. In contrast, a binary mixture of PLMA39-PMMA94 and PLMA39-d8PMMA96 nanoparticles required 8 min at this temperature before no further reduction in neutron scattering intensity could be observed. These observations suggest that the rate of copolymer chain exchange depends on the degree of polymerization of the core-forming block. Relatively slow copolymer chain exchange was also observed at 80 °C, which is below the Tg of the core-forming PMMA block as determined by DSC studies. These observations confirm rapid exchange of individual copolymer chains between sterically-stabilized nanoparticles at elevated temperature. The implications of these findings are briefly discussed in the context of PISA, which is a powerful technique for the synthesis of sterically-stabilized nanoparticles.

Electrolytic conductivity of ionic polymers in a nonpolar solvent.

The electrolytic conductivity of two electrolytes as solutions in the nonpolar solvent, n -dodecane, as a function of concentration has been studied. One was a small molecule electrolyte (tetraalkyl cation and a highly fluorinated tetraphenylborate anion), and the other was a macromolecular electrolyte (cation-containing poly(alkyl methacrylate) chain with the same anion). Two series of the macromolecular cation were prepared: one with entirely cation-containing molecules and the other with a small proportion (10%) cation-containing and the rest nonionic. The conductivity data were qualitatively similar for all systems, which formed both single ions and triple ions. The data from the two series of macromolecular electrolytes were particularly informative to understand some recent and counterintuitive electrokinetic data for particles that were stabilized by these polymers. Reducing the proportion of cationic chains in the stabilizer of the particles was found to increase their electrophoretic mobility. In the conductivity data in this study, reducing the proportion of cationic chains in solution was found to increase the magnitude of the single-ion equilibrium constant and suppress the formation of triple ions. These data should support the development of models to understand these electrokinetic results.

Spin-echo small-angle neutron scattering (SESANS) studies of diblock copolymer nanoparticles.

Poly(glycerol monomethacrylate)-poly(benzyl methacrylate) (PGMA-PBzMA) diblock copolymer nanoparticles were synthesized via polymerization-induced self-assembly (PISA) using reversible addition-fragmentation chain-transfer (RAFT) aqueous emulsion polymerization in D2O. Such PISA syntheses produce sterically-stabilized nanoparticles in situ and can be performed at relatively high copolymer concentrations (up to 50 wt%). This PGMA-PBzMA formulation is known to form only spherical nanoparticles in water using aqueous emulsion polymerization (Macromolecules, 2014, 47, 5613-5623), which makes it an ideal model system for exploring new characterization methods. The polymer micelles were characterized using small-angle X-ray scattering (SAXS) and a recently developed form of neutron scattering, spin-echo small-angle neutron scattering (SESANS). As far as we are aware, this is the first report of a study of polymer micelles by SESANS, and the data agree well with reciprocal-space scattering. Using this technique enables characterization of the concentrated, as synthesized dispersions directly without dilution, and this will provide a method to study self-assembled polymer systems that have concentration dependent morphologies, while still maintaining the advantages of scattering techniques.

Proton transfer in nonpolar solvents: an approach to generate electrolytes in aprotic media.

Stabilizing charged species in nonpolar solvents is challenging due to their low dielectric constant. As a contrast to formally ionic electrolytes, two series of acidic "potential" electrolytes have been developed in this study. These can be ionized by combining them stoichiometrically with a small molecule base in a typical nonpolar solvent, n-dodecane. The electrolytic conductivity of solutions of bis(2-ethylhexyl)phosphoric acid as mixtures with linear and branched dioctylamines and trioctylamines was measured, and the solutions were found to become increasingly conductive as the concentration increased, demonstrating that proton transfer occurred between the two species. Linear octylamines were found to be most effective at deprotonation. An acid-tipped poly(lauryl methacrylate) polymer (PLMA48-COOH) was also studied to give a polymer soluble in n-dodecane with a single ionizable group located precisely at the end of the polymer chain. Trioctylamine could successfully deprotonate this acid group. Even in an aprotic solvent, the transfer of protons between acidic and basic moieties is a useful method for controlling the properties of dissolved molecules.

Charging Poly(methyl Methacrylate) Latexes in Nonpolar Solvents: Effect of Particle Concentration.

The electrophoresis of a well-established model system of charged colloids in nonpolar solvents has been studied as a function of particle volume fraction at constant surfactant concentration. Dispersions of poly(12-hydroxystearic acid)-stabilized poly(methyl methacrylate) (PMMA) latexes in dodecane were prepared with added Aerosol OT surfactant as the charging agent. The electrophoretic mobility (µ) of the PMMA latexes is found to decrease with particle concentration. The particles are charged by a small molecule charging agent (AOT) at finite concentration, and this makes the origin of this decrease in µ unclear. There are two suggested explanations. The decrease could either be due to the reservoir of available surfactant being exhausted at high particle concentrations or the interactions between the charged particles at high particle number concentrations. Contrast-variation small-angle neutron scattering measurements of PMMA latexes and deuterated AOT-d34 surfactant in latex core contrast-matched solvent were used to study the former, and electrokinetic modeling was used to study the latter. As the same amount of AOT-d34 is found to be incorporated with the latexes at all volume fractions, the solvodynamic and electrical interactions between particles are determined to be the explanation for the decrease in mobility. These measurements show that, for small latexes, there are interactions between the charged particles at all accessible particle volume fractions and that it is necessary to account for this to accurately determine the electrokinetic ζ potential.

Drying Affects the Fiber Network in Low Molecular Weight Hydrogels.

Low molecular weight gels are formed by the self-assembly of a suitable small molecule gelator into a three-dimensional network of fibrous structures. The gel properties are determined by the fiber structures, the number and type of cross-links and the distribution of the fibers and cross-links in space. Probing these structures and cross-links is difficult. Many reports rely on microscopy of dried gels (xerogels), where the solvent is removed prior to imaging. The assumption is made that this has little effect on the structures, but it is not clear that this assumption is always (or ever) valid. Here, we use small angle neutron scattering (SANS) to probe low molecular weight hydrogels formed by the self-assembly of dipeptides. We compare scattering data for wet and dried gels, as well as following the drying process. We show that the assumption that drying does not affect the network is not always correct.

Sulfosuccinate and Sulfocarballylate Surfactants As Charge Control Additives in Nonpolar Solvents.

A series of eight sodium sulfonic acid surfactants with differently branched tails (four double-chain sulfosuccinates and four triple-chain sulfocarballylates) were studied as charging agents for sterically stabilized poly(methyl methacrylate) (PMMA) latexes in dodecane. Tail branching was found to have no significant effect on the electrophoretic mobility of the latexes, but the number of tails was found to influence the electrophoretic mobility. Triple-chain, sulfocarballylate surfactants were found to be more effective. Several possible origins of this observation were explored by comparing sodium dioctylsulfosuccinate (AOT1) and sodium trioctylsulfocarballylate (TC1) using identical approaches: the inverse micelle size, the propensity for ion dissociation, the electrical conductivity, the electrokinetic or ζ potential, and contrast-variation small-angle neutron scattering. The most likely origin of the increased ability of TC1 to charge PMMA latexes is a larger number of inverse micelles. These experiments demonstrate a small molecular variation that can be made to influence the ability of surfactants to charge particles in nonpolar solvents, and modifying molecular structure is a promising approach to developing more effective charging agents.

Celebrating Soft Matter's 10th Anniversary: Influencing the charge of poly(methyl methacrylate) latexes in nonpolar solvents.

Sterically-stabilized poly(methyl methacrylate) (PMMA) latexes dispersed in nonpolar solvents are a classic, well-studied system in colloid science. This is because they can easily be synthesized with a narrow size distribution and because they interact essentially as hard spheres. These PMMA latexes can be charged using several methods (by adding surfactants, incorporating ionizable groups, or dispersing in autoionizable solvents), and due to the low relative permittivity of the solvents (εr ≈ 2 for alkanes to εr ≈ 8 for halogenated solvents), the charges have long-range interactions. The number of studies of these PMMA particles as charged species has increased over the past ten years, after few studies immediately following their discovery. A large number of variations in both the physical and chemical properties of the system (size, concentration, surfactant type, or solvent, as a few examples) have been studied by many groups. By considering the literature on these particles as a whole, it is possible to determine the variables that have an effect on the charge of particles. An understanding of the process of charge formation will add to understanding how to control charge in nonaqueous solvents as well as make it possible to develop improved technologically relevant applications for charged polymer nanoparticles.

Low-surface energy surfactants with branched hydrocarbon architectures.

Surface tensiometry and small-angle neutron scattering have been used to characterize a new class of low-surface energy surfactants (LSESs), "hedgehog" surfactants. These surfactants are based on highly branched hydrocarbon (HC) chains as replacements for environmentally hazardous fluorocarbon surfactants and polymers. Tensiometric analyses indicate that a subtle structural modification in the tails and headgroup results in significant effects on limiting surface tensions γcmc at the critical micelle concentration: a higher level of branching and an increased counterion size promote an effective reduction of surface tension to low values for HC surfactants (γcmc ∼ 24 mN m(-1)). These LSESs present a new class of potentially very important materials, which form lamellar aggregates in aqueous solutions independent of dilution.

Shape transitions in supercritical CO2 microemulsions induced by hydrotropes.

The ability to induce morphological transitions in water-in-oil (w/o) and water-in-CO2 (w/c) microemulsions stabilized by a trichain anionic surfactant 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2-sulfonate (TC14) with simple hydrotrope additives has been investigated. High-pressure small-angle neutron scattering (SANS) has revealed the addition of a small mole fraction of hydrotrope can yield a significant elongation in the microemulsion water droplets. For w/o systems, the degree of droplet growth was shown to be dependent on the water content, the hydrotrope mole fraction, and chemical structure, whereas for w/c microemulsions a similar, but less significant, effect was seen. The expected CO2 viscosity increase from such systems has been calculated and compared to related literature using fluorocarbon chain surfactants. This represents the first report of hydrotrope-induced morphology changes in w/c microemulsions and is a significant step forward toward the formation of hydrocarbon worm-like micellar assemblies in this industrially relevant solvent.

Interaction between surfactants and colloidal latexes in nonpolar solvents studied using contrast-variation small-angle neutron scattering.

The interaction between deuterium-labeled Aerosol OT surfactant (AOT-d34) and sterically stabilized poly(methyl methacrylate) (PMMA) latex particles dispersed in nonpolar solvents has been studied using contrast-variation small-angle neutron scattering (CV-SANS). The electrophoretic mobilities (µ) of the latexes have been measured by phase-analysis light scattering, indicating that µ is negative. Two analogues of the stabilizers for the particles have been studied as free polymers in the absence of PMMA latexes: poly(12-hydroxystearic acid) (PHSA) polyester and poly(methyl methacrylate)-graft-poly(12-hydroxystearic acid) (PMMA-graft-PHSA) stabilizer copolymer. The scattering from both PHSA in dodecane and PMMA-graft-PHSA in toluene is consistent with extended polymer chains in good solvents. In dodecane, PMMA-graft-PHSA forms polymer micelles, and SANS is consistent with ellipsoidal aggregates formed of around 50 polymer chains. CV-SANS measurements were performed by measuring SANS from systems of PHSA, PMMA-graft-PHSA, and PMMA latexes with 10 and 100 mM surfactant solutions of AOT-d34 in both polymer/particle and AOT contrast-matched solvent. No excess scattering above the polymer or surfactant was found for PHSA in dodecane or PMMA-graft-PHSA in dodecane and toluene. This indicates that AOT does not significantly interact with the free polymers. Excess scattering was observed for systems with AOT-d34 and PMMA latexes dispersed in particle contrast-matched dodecane, consistent with the penetration of AOT into the PMMA latexes. This indicates that AOT does not interact preferentially with the stabilizing layers but, rather, is present throughout the colloids. Previous research ( Langmuir 2010, 26, 6967-6976 ) suggests that AOT surfactant is located in the latex PHSA-stabilizer layer, but all the results in this study are consistent with AOT poorly interacting with alkyl-stabilizer polymers.

Human antimicrobial peptide inactivation mechanism of enveloped viruses.

HYPOTHESIS: Enveloped viruses are pivotal in causing various illnesses, including influenza and COVID-19. The antimicrobial peptide LL-37, a critical part of the human innate immune system, exhibits potential as an antiviral agent capable of thwarting these viral threats. Its mode of action involves versatile and non-specific interactions that culminate in dismantling the viral envelope, ultimately rendering the viruses inert. However, the exact mechanism of action is not yet understood. EXPERIMENTS: Here, the mechanism of LL-37 triggered changes in the structure and function of an enveloped virus is investigated. The bacteriophage "Phi6" is used as a surrogate for pathogenic enveloped viruses. Small angle X-ray and neutron scattering combined with light scattering techniques demonstrate that LL-37 actively integrates into the virus's lipid envelope. FINDINGS: LL-37 addition to Phi6 leads to curvature modification in the lipid bilayer, ultimately separating the envelope from the nucleocapsid. Additional biological assays confirm the loss of virus infectivity in the presence of LL-37, which coincides with the structural transformations. The results provide a fundamental understanding of the structure-activity relationship related to enveloped viruses. The knowledge of peptide-virus interactions can guide the design of future peptide-based antiviral drugs and therapies.

Evidence for a critical micelle concentration of surfactants in hydrocarbon solvents.

The concentration-dependent aggregation of two surfactants, anionic sodium dioctylsulfosuccinate (Aerosol OT or AOT) and nonionic pentaethylene glycol monododecyl ether (C12E5), has been studied in cyclohexane-D12 using small-angle neutron scattering (SANS). A clear monomer-to-aggregate transition has been observed for both surfactants, spherical inverse micelles for AOT and hank-like micelles for C12E5. This suggests that a critical micelle concentration exists for surfactants of these kinds in nonpolar solvents. The nature of the transition is different for the two surfactants. AOT aggregates are the same size and shape with decreasing concentration until a sharp critical micelle concentration, after which they cannot be detected. However, C12E5 aggregates gradually decrease in size. These differences demonstrate that the strength of the solvophobic effect can influence the formation of surfactant aggregates in nonaqueous solvents.

Controlling colloid charge in nonpolar liquids with surfactants.

The formation of ions in nonpolar solvents (with relative permittivity ε(r) of approximately 2) is more difficult than in polar liquids; however, these charged species play an important role in many applications, such as electrophoretic displays. The low relative permittivities of these solvents mean that charges have to be separated by large distances to be stable (approximately 28 nm or 40 times that in water). The inverse micelles formed by surfactants in these solvents provide an environment to stabilize ions and charges. Common surfactants used are sodium dioctylsulfosuccinate (Aerosol OT or AOT), polyisobutylene succinimide, sorbitan oleate, and zirconyl 2-ethyl hexanoate. The behavior of charged inverse micelles has been studied on both the bulk and on the microscopic scale and can be used to determine the motion of the micelles, their structure, and the nature of the electrostatic double layer. Colloidal particles are only weakly charged in the absence of surfactant, but in the presence of surfactants, many types, including polymers, metal oxides, carbon blacks, and pigments, have been observed to become positively or negatively charged. Several mechanisms have been proposed as the origin of surface charge, including acid-base reactions between the colloid and the inverse micelle, preferential adsorption of charged inverse micelles, or dissolution of surface species. While most studies vary only the concentration of surfactant, systematic variation of the particle surface chemistry or the surfactant structure have provided insight into the origin of charging in nonpolar liquids. By carefully varying system parameters and working to understand the interactions between surfactants and colloidal surfaces, further advances will be made leading to better understanding of the origin of charge and to the development of more effective surfactants.

The relationship between ultra-small-angle X-ray scattering and viscosity measurements of casein micelles in skim milk concentrates.

Skim milk concentrates have important applications in the dairy industry, often as intermediate ingredients. Concentration of skim milk by reverse osmosis membrane filtration induces water removal, which reduces the free volume between the colloidal components, in particular the casein micelles. Thermal treatment before or after concentration impacts the morphology of casein micelles. These changes affect the flow behavior and viscosity, but the consequences for supermicellar structure have not been elucidated. In the present study, skim milk concentrates with different total solid contents from 8.7% (control) up to 22.8% (w/w), prepared by reverse osmosis membrane filtration of non-heated and pasteurized skim milk, were heat treated at 75 °C for 18 s, and compared with non-heated concentrates. The structure of the concentrates was studied using Ultra Small Angle X-ray Scattering (USAXS), and the viscosity of concentrates was measured. The USAXS intensity I(q) was fitted at small and intermediate q-regions (0.0005 < q < 0.003 Å-1 and 0.0035 < q < 0.03 Å-1, respectively) with a power law. The value of the power law exponent was used to assess the heat- and concentration-induced aggregation of the milk solids and correlate it with the apparent viscosity. The results showed that increased viscosity of skim milk concentrates, due to water removal and heat-load, can be explained by increased aggregation of the casein micelles into elongated aggregates and increased smoothening of the casein micelle surface.

Molecular exchange in spherical diblock copolymer colloids synthesised by polymerisation-induced self-assembly.

HYPOTHESIS: To study molecular exchange between colloids requires the preparation of suitably labelled species. Deuterium isotopic labelling has been used to prepare two chemically identical yet isotopically distinguishable poly(lauryl methacrylate)-poly(methyl methacrylate) (PLMA-PMMA) diblock copolymer colloids by polymerisation-induced self-assembly (PISA) directly in an alkane solvent. Molecular exchange should be detectable by performing small-angle neutron scattering (SANS) measurements on the dispersions. EXPERIMENTS: SANS measurements were performed on fully hydrogenous PLMA39-PMMA57 and deuterated core PLMA39-P(MMA-d8)57 colloids. They were mixed in equal amounts and heated to determine if molecular exchange occurred. PISA syntheses are often thermally initiated, and diblock copolymers self-assemble at elevated temperature, making this an important parameter to study. Experimental data for the mixture were compared to predicted curves for exchanged and non-exchanged colloids. FINDINGS: The scattering of a mixture of fully hydrogenous and deuterated core copolymers does not disappear upon molecular exchange, due to the remaining contrast between the stabiliser and the core and solvent even after the cores fully exchange. By simultaneously fitting the SANS data from dispersions before mixing and using these parameters to constrain fitting the SANS data of mixtures, the molecular exchange between diblock copolymer micelles upon heating is clearly observed.