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.

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.

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.

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.

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.

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.

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.

The extent of counterion dissociation at the interface of cationic diblock copolymer nanoparticles in non-polar solvents.

HYPOTHESIS: Diblock copolymer nanoparticles prepared in non-polar solvents that are sterically stabilized but possess ionic functionality from the inclusion of cationic comonomers in the stabilizer shell are known to exhibit complex electrokinetic behavior (Chem. Sci. 9 (2018) 922-934). For example, core-shell nanoparticles with cationic comonomers located solely within the shell layer have lower magnitude electrophoretic mobilities than nanoparticles containing the same cationic comonomers located within the core, whereas nanoparticles prepared using a minor fraction of steric stabilizer chains containing cationic comonomer repeat units have comparable electrophoretic mobilities to nanoparticles prepared with this cationic comonomer solely located within the core. We hypothesize that these observations can be explained in terms of the strength of the Coulombic interaction between counterions and the nanoparticle interface. EXPERIMENTS: The highly-fluorinated anionic counterion associated with these cationic nanoparticles is studied by 19F nuclear magnetic resonance (NMR) spectroscopy in n-dodecane. This revealed only one type of 19F environment for a soluble macromolecular cation (the oil-soluble steric stabilizer chains used to prepare the nanoparticles), whereas two distinct environments were observed for the sterically-stabilized cationic nanoparticles. Both 19F diffusion NMR and 19F-13C heteronuclear single quantum correlation (HSQC) measurements support the existence of two environments for this counterion. FINDINGS: The existence of two distinct 19F environments for the highly-fluorinated anion associated with the sterically-stabilized nanoparticles demonstrates the presence of spectroscopically distinguishable populations of ion pairs and of fully dissociated free anions. 19F NMR spectra recorded for sterically-stabilized nanoparticles with a fully ionic shell (all stabilizer chains containing the cationic comonomer) and those with a partly ionic shell (10% of stabilizer chains containing the cationic comonomer) reveal a higher proportion of dissociated anions in the partly ionic case. This suggests a stronger Coulombic interaction between counterions and the cationic interface when the shell is fully ionic, which accounts for the observed reduction in the magnitude of the electrophoretic mobility.

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.

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.

Refractive index matched, nearly hard polymer colloids.

Refractive index matched particles serve as essential model systems for colloid scientists, providing nearly hard spheres to explore structure and dynamics. The poly(methyl methacrylate) latexes typically used are often refractive index matched by dispersing them in binary solvent mixtures, but this can lead to undesirable changes, such as particle charging or swelling. To avoid these shortcomings, we have synthesized refractive index matched colloids using polymerization-induced self-assembly (PISA) rather than as polymer latexes. The crucial difference is that these diblock copolymer nanoparticles consist of a single core-forming polymer in a single non-ionizable solvent. The diblock copolymer chosen was poly(stearyl methacrylate)-poly(2,2,2-trifluoroethyl methacrylate) (PSMA-PTFEMA), which self-assembles to form PTFEMA core spheres in n-alkanes. By monitoring scattered light intensity, n-tetradecane was found to be the optimal solvent for matching the refractive index of such nanoparticles. As expected for PISA syntheses, the diameter of the colloids can be controlled by varying the PTFEMA degree of polymerization. Concentrated dispersions were prepared, and the diffusion of the PSMA-PTFEMA nanoparticles as a function of volume fraction was measured. These diblock copolymer nanoparticles are a promising new system of transparent spheres for future colloidal studies.

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.

Synthesis and electrokinetics of cationic spherical nanoparticles in salt-free non-polar media.

Cationic diblock copolymer nanoparticles have been prepared in n-dodecane via polymerization-induced self-assembly (PISA). A previously reported poly(stearyl methacrylate)-poly(benzyl methacrylate) (PSMA-PBzMA) PISA formulation (Chem. Sci. 2016, 7, 5078-5090) was modified by statistically copolymerizing an oil-soluble cationic methacrylic monomer, (2-(methacryloyloxy)ethyl)trimethylammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, with either SMA or BzMA, to produce either charged shell or charged core nanoparticles. The electrokinetics were studied as a function of many variables (function of volume function, particle size, solvent viscosity, and number of ions per chain). These data are consistent with electrophoresis controlled by counterion condensation, which is typically observed in salt-free media. However, there are several interesting and unexpected features of interest. In particular, charged shell nanoparticles have a lower electrophoretic mobility than the equivalent charged core nanoparticles, and the magnitude of the electrophoretic mobility increases as the fraction of cationic stabilizer chains in the shell layer is reduced. These results show that cationic PSMA-PBzMA spheres provide an interesting new example of electrophoretic nanoparticles in non-polar solvents. Moreover, they should provide an ideal model system to evaluate new electrokinetic theories.

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.

Electrolyte-induced Instability of Colloidal Dispersions in Nonpolar Solvents.

Dispersions of poly(methyl methacrylate) (PMMA) latexes were prepared in a low dielectric, nonpolar solvent (dodecane) both with and without the oil-soluble electrolyte, tetradodecylammonium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. For dispersions with a high concentration of background electrolyte, the latexes become colloidally unstable and sediment in a short period of time (<1 h). This is completely reversible upon dilution. Instability of the dispersions is due to an apparent attraction between the colloids, directly observed using optical tweezers by bringing optically trapped particles into close proximity. Simple explanations generally used by colloid scientists to explain loss of stability (charge screening or stabilizer collapse) are insufficient to explain this observation. This unexpected interaction seems, therefore, to be a consequence of the materials that can be dispersed in low dielectric media and is expected to have ramifications for studying colloids in such solvents.

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.

The internal structure of poly(methyl methacrylate) latexes in nonpolar solvents.

HYPOTHESIS: Poly(methyl methacrylate) (PMMA) latexes in nonpolar solvents are an excellent model system to understand phenomena in low dielectric media, and understanding their internal structure is critical to characterizing their performance in both fundamental studies of colloidal interactions and in potential industrial applications. Both the PMMA cores and the poly(12-hydroxystearic acid) (PHSA) shells of the latexes are known to be penetrable by solvent and small molecules, but the relevance of this for the properties of these particles is unknown. EXPERIMENTS: These particles can be prepared in a broad range of sizes, and two PMMA latexes dispersed in n-dodecane (76 and 685nm in diameter) were studied using techniques appropriate to their size. Small-angle scattering (using both neutrons and X-rays) was used to study the small latexes, and analytical centrifugation was used to study the large latexes. These studies enabled the calculation of the core densities and the amount of solvent in the stabilizer shells for both latexes. Both have consequences on interpreting measurements using these latexes. FINDINGS: The PHSA shells are highly solvated (∼85% solvent by volume), as expected for effective steric stabilizers. However, the PHSA chains do contribute to the intensity of neutron scattering measurements on concentrated dispersions and cannot be ignored. The PMMA cores have a slightly lower density than PMMA homopolymer, which shows that only a small free volume is required to allow small molecules to penetrate into the cores. Interestingly, the observations are essentially the same, regardless of the size of the particle; these are general features of these polymer latexes. Despite the latexes being used as a model physical system, the internal chemical structure is complex and must be fully considered when characterizing them.

A Critical Appraisal of RAFT-Mediated Polymerization-Induced Self-Assembly.

Recently, polymerization-induced self-assembly (PISA) has become widely recognized as a robust and efficient route to produce block copolymer nanoparticles of controlled size, morphology, and surface chemistry. Several reviews of this field have been published since 2012, but a substantial number of new papers have been published in the last three years. In this Perspective, we provide a critical appraisal of the various advantages offered by this approach, while also pointing out some of its current drawbacks. Promising future research directions as well as remaining technical challenges and unresolved problems are briefly highlighted.

Magnetic surfactants as molecular based-magnets with spin glass-like properties.

This paper reports the use of muon spin relaxation spectroscopy to study how the aggregation behavior of magnetic surfactants containing lanthanide counterions may be exploited to create spin glass-like materials. Surfactants provide a unique approach to building in randomness, frustration and competing interactions into magnetic materials without requiring a lattice of ordered magnetic species or intervening ligands and elements. We demonstrate that this magnetic behavior may also be manipulated via formation of micelles rather than simple dilution, as well as via design of surfactant molecular architecture. This somewhat unexpected result indicates the potential of using novel magnetic surfactants for the generation and tuning of molecular magnets.