Synthesis and Characterization of Titanium Nitride-Carbon Composites and Their Use in Lithium-Ion Batteries.

This work focuses on the synthesis of titanium nitride-carbon (TiN-carbon) composites by the thermal decomposition of a titanyl phthalocyanine (TiN(TD)) precursor into TiN. The synthesis of TiN was also performed using the sol-gel method (TiN(SG)) of an alkoxide/urea. The structure and morphology of the TiN-carbon and its precursors were characterized by XRD, FTIR, SEM, TEM, EDS, and XPS. The FTIR results confirmed the presence of the titanium phthalocyanine (TiOPC) complex, while the XRD data corroborated the decomposition of TiOPC into TiN. The resultant TiN exhibited a cubic structure with the FM3-M lattice, aligning with the crystal system of the synthesized TiN via the alkoxide route. The XPS results indicated that the particles synthesized from the thermal decomposition of TiOPC resulted in the formation of TiN-carbon composites. The TiN particles were present as clusters of small spherical particles within the carbon matrix, displaying a porous sponge-like morphology. The proposed thermal decomposition method resulted in the formation of metal nitride composites with high carbon content, which were used as anodes for Li-ion half cells. The TiN-carbon composite anode showed a good specific capacity after 100 cycles at a current density of 100 mAg-1.

Particle Dynamics in a Diblock-Copolymer-Based Dodecagonal Quasicrystal and Its Periodic Approximant by X-Ray Photon Correlation Spectroscopy.

Temperature-dependent x-ray photon correlation spectroscopy (XPCS) measurements are reported for a binary diblock-copolymer blend that self-assembles into an aperiodic dodecagonal quasicrystal and a periodic Frank-Kasper σ phase approximant. The measured structural relaxation times are Bragg scattering wavevector independent and are 5 times faster in the dodecagonal quasicrystal than the σ phase, with minimal temperature dependence. The underlying dynamical relaxations are ascribed to differences in particle motion at the grain boundaries within each of these tetrahedrally close-packed assemblies. These results identify unprecedented particle dynamics measurements of tetrahedrally coordinated micellar block polymers, thus expanding the application of XPCS to ordered soft materials.

Cylinders-in-Undulating-Lamellae Morphology from ABC Bottlebrush Block Terpolymers.

Block polymer self-assembly affords a versatile bottom-up strategy to develop materials with the desired properties dictated by specific symmetries and dimensions. Owing to distinct properties compared with linear counterparts, bottlebrush block polymers with side chains densely grafted on a backbone have attracted extensive attention. However, the morphologies found in bottlebrush block polymers so far are limited, and only lamellar and cylindrical ordered phases have been reported in diblock bottlebrushes. The absence of complex morphologies, such as networks, might originate from the intrinsically stiff backbone architecture. We experimentally investigated the morphologies of nonfrustrated ABC bottlebrush block terpolymers, based on two chemistries, poly(ethylene-alt-propylene)-b-polystyrene-b-poly(dl-lactic acid) (PEP-PS-PLA) and PEP-b-PS-b-poly(ethylene oxide) (PEP-PS-PEO), synthesized by ring-opening metathesis polymerization of norbornene-terminated macromonomers. Structural characterization based on small-angle X-ray scattering and transmission electron microscopy measurements revealed an unprecedented cylinders-in-undulating-lamellae (CUL) morphology with p2 symmetry for both systems. Additionally, automated liquid chromatography was employed to fractionate the PEP-PS-PLA bottlebrush polymer, leading to fractions with a spectrum of morphologies, including the CUL. These findings underscore the significance of macromolecular dispersity in nominally narrow dispersity bottlebrush polymers while demonstrating the power of this fractionation technique.

Crystallization Inhibition in Molecular Liquids by Polymers above the Overlap Concentration (c*): Delay of the First Nucleation Event.

Low concentration polymer additives can significantly alter crystal growth kinetics of molecular liquids and glasses. However, the effect of polymer concentration on nucleation kinetics remains poorly understood. Based on an experimentally determined first nucleation time (time to form the first critical nucleus, t0), we show that the polymer overlap concentration, c*, where polymer coils in the molecular liquid start to overlap with each other, is a critical polymer concentration for efficient inhibition of crystallization of a molecular liquid. The value of t0 is approximately equal to that of the neat molecular liquid when the polymer concentration, c, is below c*, but increases significantly when c > c*. This finding is relevant for effective polymer screening and performance prediction of engineered multicomponent amorphous materials, particularly pharmaceutical amorphous solid dispersions.

Self-Assembly of Unusually Stable Thermotropic Network Phases by Cellobiose-Based Guerbet Glycolipids.

Bicontinuous thermotropic liquid crystal (LC) materials, e.g., double gyroid (DG) phases, have garnered significant attention due to the potential utility of their 3D network structures in wide-ranging applications. However, the utility of these materials is significantly constrained by the lack of robust molecular design rules for shape-filling amphiphiles that spontaneously adopt the saddle curvatures required to access these useful supramolecular assemblies. Toward this aim, we synthesized anomerically pure Guerbet-type glycolipids bearing cellobiose head groups and branched alkyl tails and studied their thermotropic LC self-assembly. Using a combination of differential scanning calorimetry, polarized optical microscopy, and small-angle X-ray scattering, our studies demonstrate that Guerbet cellobiosides exhibit a strong propensity to self-assemble into DG morphologies over wide thermotropic phase windows. The stabilities of these assemblies sensitively depend on the branched alkyl tail structure and the anomeric configuration of the glycolipid in a previously unrecognized manner. Complementary molecular simulations furnish detailed insights into the observed self-assembly characteristics, thus unveiling molecular motifs that foster network phase self-assembly that will enable future designs and applications of network LC materials.

Discovery of Kinetic Trapping of Poloxamers inside Liposomes via Thermal Treatment.

Poloxamers, a class of biocompatible, commercially available amphiphilic block polymers (ABPs) comprising poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) blocks, interact with phospholipid bilayers, resulting in altered mechanical and surface properties. These block copolymers are useful in a variety of applications including therapeutics for Duchenne muscular dystrophy, as cell membrane stabilizers, and for drug delivery, as liposome surface modifying agents. Hydrogen bonding between water and oxygen atoms in PEO and PPO units results in thermoresponsive behavior because the bound water shell around both blocks dehydrates as the temperature increases. This motivated an investigation of poloxamer-lipid bilayer interactions as a function of temperature and thermal history. In this study, we applied pulsed-field-gradient NMR spectroscopy to measure the fraction of chains bound to 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) liposomes between 10 and 50 °C. We measured an (11 ± 3)-fold increase in binding affinity at 37 °C relative to 27 °C. Moreover, following incubation at 37 °C, it takes weeks for the system to re-equilibrate at 25 °C. Such slow desorption kinetics suggests that at elevated temperatures polymer chains can pass through the bilayer and access the interior of the liposomes, a mechanism that is inaccessible at lower temperatures. We propose a molecular mechanism to explain this effect, which could have important ramifications on the cellular distribution of ABPs and could be exploited to modulate the mechanical and surface properties of liposomes and cell membranes.

Effect of poly[oligo(ethylene glycol) methyl ether methacrylate] side chain length on the brush swelling behavior in A/B/A-B ternary blends with polystyrene.

The phase behavior of ternary blends composed of two homopolymers (A, B) and their corresponding diblock copolymer (A-B) has been widely studied, with emphasis on the volumetrically symmetric isopleth and the formation of bicontinuous microemulsions. However, almost all the previous studies employed linear polymers, and little is known about the impact of polymer architecture on the phase behavior of such ternary blends. Here, we report the self-assembly of three sets of ternary blends of polystyrene (PS) and poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMAn), with different lengths of oligo(ethylene glycol) side chains n. Small-angle X-ray scattering was used to probe the phase behavior at different compositions and temperatures. The order-to-disorder transition temperature was found to be impacted by the side chain length. It was also observed that longer side chains lead to poorer miscibility of homopolymers in the corresponding block, resulting in a more "dry-brush" like swelling behavior.

Effect of Poloxamer Binding on the Elasticity and Toughness of Model Lipid Bilayers.

Poloxamers, also known by their trade name, Pluronics, are known to mitigate damage to cellular membranes. However, the mechanism underlying this protection is still unclear. We investigated the effect of poloxamer molar mass, hydrophobicity, and concentration on the mechanical properties of giant unilamellar vesicles, composed of 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine, using micropipette aspiration (MPA). Properties including the membrane bending modulus (κ), stretching modulus (K), and toughness are reported. We found that poloxamers tend to decrease K, with an impact largely dictated by their membrane affinity, i.e., both a high molar mass and less hydrophilic poloxamers depress K at lower concentrations. However, a statistically significant effect on κ was not observed. Several poloxamers studied here showed evidence of membrane toughening. Additional pulsed-field gradient NMR measurements provided insight into how polymer binding affinity connects to the trends observed by MPA. This model study provides important insights into how poloxamers interact with lipid membranes to further understanding of how they protect cells from various types of stress. Furthermore, this information may prove useful for the modification of lipid vesicles for other applications, including use in drug delivery or as nanoreactors.

Photocrosslinkable Polymeric Bicontinuous Microemulsions.

We present an approach to photocrosslink bicontinuous microemulsions derived from ternary blends of poly(methoxyethyl acrylate) (PM, Mn = 4200 g/mol), poly(hexyl methacrylate-co-coumarin methacrylate) (PHC, Mn = 6800 g/mol), and PM-b-PHC diblock polymer (Mn = 19,400 g/mol) in a phase-selective manner, enabling structural characterization at an unprecedented level of detail. This strategy utilizes the [2 + 2] photodimerization reaction of coumarin derivatives to covalently crosslink blends without the use of harsh reagents or disruptive thermal treatment, thus preserving the intricate network structure throughout curing. The resulting crosslinked bicontinuous microemulsions exhibited rubbery behavior at elevated temperatures, achieving an elastic shear modulus of nearly 1 MPa at 70 °C, owing to the presence of the three-dimensional co-continuous network morphology. The dimensional stabilization afforded by crosslinking further allowed the microstructure to be directly imaged by scanning electron microscopy and atomic force microscopy. Contrary to recent theoretical findings, the BµE appears in a wide temperature and compositional window, suggesting that it is a robust feature of these blends. As a proof of concept demonstrating both the utility of bicontinuous microemulsion-derived materials and versatility of this strategy toward broader applications in energy storage and transport, the uncrosslinked portion of a cured blend was extracted by washing and replaced with an ionic liquid; the resultant heterogeneous solid electrolyte exhibited a room-temperature conductivity of 2 mS/cm, approximately one-quarter that of the pure ionic liquid.

Molecular homing and retention of muscle membrane stabilizing copolymers by non-invasive optical imaging in vivo.

First-in-class membrane stabilizer Poloxamer 188 (P188) has been shown to confer membrane protection in an extensive range of clinical conditions; however, elements of the systemic distribution and localization of P188 at the organ, tissue, and muscle fiber levels in vivo have not yet been elucidated. Here we used non-invasive fluorescence imaging to directly visualize and track the distribution and localization of P188 in vivo. The results demonstrated that the Alx647 probe did not alter the fundamental properties of P188 to protect biological membranes. Distribution kinetics in mdx mice demonstrated that Alx647 did not interface with muscle membranes and had fast clearance kinetics. In contrast, the distribution kinetics for P188-Alx647 was significantly slower, indicating a dramatic depot and retention effect of P188. Results further demonstrated the significant retention of P188-Alx647 in the skeletal muscle of mdx mice, showing a significant genotype effect with a higher fluorescence signal in the mdx muscles over BL10 mice. High-resolution optical imaging provided direct evidence of P188 surrounding the sarcolemma of skeletal and cardiac muscle cells. Taken together, these findings provide direct evidence of muscle-disease-dependent molecular homing and retention of synthetic copolymers in striated muscles thereby facilitating advanced studies of copolymer-membrane association in health and disease.

Effect of Bottlebrush Poloxamer Architecture on Binding to Liposomes.

Poloxamers─triblock copolymers consisting of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO)─have demonstrated cell membrane stabilization efficacy against numerous types of stress. However, the mechanism responsible for this stabilizing effect remains elusive, hindering engineering of more effective therapeutics. Bottlebrush polymers have a wide parameter space and known relationships between architectural parameters and polymer properties, enabling their use as a tool for mechanistic investigations of polymer-lipid bilayer interactions. In this work, we utilized a versatile synthetic platform to create novel bottlebrush analogues to poloxamers and then employed pulsed-field-gradient NMR and an in vitro osmotic stress assay to explore the effect of bottlebrush architectural parameters on binding to, and protection of, model phospholipid bilayers. We found that the binding affinity of a bottlebrush poloxamer (BBP) (B-E1043P515, Mn ≈ 26 kDa) is about 3 times higher than a linear poloxamer with a similar composition and number of PPO units (L-E93P54E93, Mn ≈ 11 kDa). Furthermore, BBP binding is sensitive to overall molecular weight, side-chain length, and architecture (statistical versus block). Finally, all tested BBPs exhibit a protective effect on cell membranes under stress at sub-µM concentrations. As the factors controlling membrane affinity and protection efficacy of bottlebrush poloxamers are not understood, these results provide important insight into how they adhere to and stabilize a lipid bilayer surface.

A Rheological Approach for Predicting Physical Stability of Amorphous Solid Dispersions.

Miscibility is an important indicator of physical stability against crystallization of amorphous solid dispersions (ASDs). Currently available methods for miscibility determination have both theoretical and practical limitations. Here we report a method of miscibility determination based on the overlap concentration, c*, which can be conveniently determined from the viscosity-composition diagram. The determined c* values for ASDs of two model drugs, celecoxib and loratadine, with four different grades of polyvinylpyrrolidone (PVP), were correlated strongly with the physical stability of ASDs. This result suggests potential application of the c* concept in guiding the design of stable high drug loaded ASD formulations. A procedure is provided to facilitate broader adoption of this methodology. The procedure is easy to apply and widely applicable for thermally stable binary drug/polymer combinations.

Dynamics and Equilibration Mechanisms in Block Copolymer Particles.

Self-assembly of block copolymers into interesting and useful nanostructures, in both solution and bulk, is a vibrant research arena. While much attention has been paid to characterization and prediction of equilibrium phases, the associated dynamic processes are far from fully understood. Here, we explore what is known and not known about the equilibration of particle phases in the bulk, and spherical micelles in solution. The presumed primary equilibration mechanisms are chain exchange, fusion, and fragmentation. These processes have been extensively studied in surfactants and lipids, where they occur on subsecond time scales. In contrast, increased chain lengths in block copolymers create much larger barriers, and time scales can become prohibitively slow. In practice, equilibration of block copolymers is achievable only in proximity to the critical micelle temperature (in solution) or the order-disorder transition (in the bulk). Detailed theories for these processes in block copolymers are few. In the bulk, the rate of chain exchange can be quantified by tracer diffusion measurements. Often the rate of equilibration, in terms of number density and aggregation number of particles, is much slower than chain exchange, and consequently observed particle phases are often metastable. This is particularly true in regions of the phase diagram where Frank-Kasper phases occur. Chain exchange in solution has been explored quantitatively by time-resolved SANS, but the results are not well captured by theory. Computer simulations, particularly via dissipative particle dynamics, are beginning to shed light on the chain escape mechanism at the molecular level. The rate of fragmentation has been quantified in a few experimental systems, and TEM images support a mechanism akin to the anaphase stage of mitosis in cells, via a thin neck that pinches off to produce two smaller micelles. Direct measurements of micelle fusion are quite rare. Suggestions for future theoretical, computational, and experimental efforts are offered.

Core-Shell Gyroid in ABC Bottlebrush Block Terpolymers.

Block polymer self-assembly provides a versatile platform for creating useful materials endowed with three-dimensional periodic network morphologies that support orthogonal physical properties such as high ionic conductivity and a high elastic modulus. However, coil configurations limit conventional linear block polymers to finite ordered network dimensions, which are further restricted by slow self-assembly kinetics at high molecular weights. A bottlebrush architecture can circumvent both shortcomings owing to extended backbone configurations due to side chain crowding and molecular dynamics substantially free of chain entanglements. However, until now, network morphologies have not been reported in AB bottlebrush block copolymers, notwithstanding favorable mean-field predictions. We explored the phase behavior by small-angle X-ray scattering of 133 poly(ethylene-alt-propylene)-b-polystyrene (PEP-PS) diblock and PEP-PS-PEO triblock bottlebrush copolymers prepared by ring-opening metathesis polymerization (ROMP) of norbornene-functionalized poly(ethylene-alt-propylene) (PEP), poly(styrene) (PS), and poly(ethylene oxide) (PEO) macromonomers with total backbone degrees of polymerization Nbb between 20 and 40. The PEP-PS diblocks exhibited only cylindrical and lamellar morphologies over the composition range of ca. 30-70%. However, addition of variable-length bottlebrush PEO blocks to diblocks containing 30-50% PS led to the formation of a substantial core-shell double gyroid (GYR) phase window containing 20 bottlebrush triblock specimens, which is the focus of this report. Encouragingly, the GYR unit cell dimensions increased as d ∼ Nbb0.92, portending the ability to access larger network dimensions than previously obtained with linear AB or ABC block polymers. This work highlights extraordinary opportunities associated with applying facile ROMP chemistry to multiblock bottlebrush polymers.

Stabilizing a Double Gyroid Network Phase with 2 nm Feature Size by Blending of Lamellar and Cylindrical Forming Block Oligomers.

Molecular dynamics simulations are used to study binary blends of an AB-type diblock and an AB2-type miktoarm triblock amphiphiles (also known as high-χ block oligomers) consisting of sugar-based (A) and hydrocarbon (B) blocks. In their pure form, the AB diblock and AB2 triblock amphiphiles self-assemble into ordered lamellar (LAM) and cylindrical (CYL) structures, respectively. At intermediate compositions, however, the AB2-rich blend (0.2 ≤ x AB ≤ 0.4) forms a double gyroid (DG) network, whereas perforated lamellae (PL) are observed in the AB-rich blend (0.5 ≤ x AB ≤ 0.8). All of the ordered mesophases present domain pitches under 3 nm, with 1 nm feature sizes for the polar domains. Structural analyses reveal that the nonuniform interfacial curvatures of DG and PL structures are supported by local composition variations of the LAM- and CYL-forming amphiphiles. Self-consistent mean field theory calculations for blends of related AB and AB2 block polymers also show the DG network at intermediate compositions, when A is the minority block, but PL is not stable. This work provides molecular-level insights into how blending of shape-filling molecular architectures enables network phase formation with extremely small feature sizes over a wide composition range.

Synthesis and Micellization of Bottlebrush Poloxamers.

Bottlebrush polymers are characterized by an expansive parameter space, including graft length and spacing along the backbone, and these features impact various structural and physical properties such as molecular diffusion and bulk viscosity. In this work, we report a synthetic strategy for making grafted block polymers with poly(propylene oxide) and poly(ethylene oxide) side chains, bottlebrush analogues of poloxamers. Combined anionic and sequential ring-opening metathesis polymerization yielded low dispersity polymers, at full conversion of the macromonomers, with control over graft length, graft end-groups, and overall molecular weight. A set of bottlebrush poloxamers (BBPs), with identical graft lengths and composition, was synthesized over a range of molecular weights. Dynamic light scattering and transmission electron microscopy were used to characterize micelle formation in aqueous buffer. The critical micelle concentration scales exponentially with overall molecular weight for both linear and bottlebrush poloxamers; however, the bottlebrush architecture shifts micelle formation to a much higher concentration at a comparable molecular weight. Consequently, BBPs can exist in solution as unimers at significantly higher molecular weights and concentrations than the linear analogues.

Improved nanoformulation and bio-functionalization of linear-dendritic block copolymers with biocompatible ionic liquids.

Linear-dendritic block copolymers (LDBCs) have emerged as promising materials for drug delivery applications, with their hybrid structure exploiting advantageous properties of both linear and dendritic polymers. LDBCs have promising encapsulation efficiencies that can be used to encapsulate both hydrophobic and hydrophilic dyes for bioimaging, cancer therapeutics, and small biomolecules. Additionally, LDBCS can be readily functionalized with varying terminal groups for more efficient targeted delivery. However, depending on structural composition and surface properties, LDBCs also exhibit high dispersities (D), poor shelf-life, and potentially high cytotoxicity to non-target interfacing blood cells during intravenous drug delivery. Here, we show that choline carboxylic acid-based ionic liquids (ILs) electrostatically solvate LDBCs by direct dissolution and form stable and biocompatible IL-integrated LDBC nano-assemblies. These nano-assemblies are endowed with red blood cell-hitchhiking capabilities and show altered cellular uptake behavior ex vivo. When modified with choline and trans-2-hexenoic acid, IL-LDBC dispersity dropped by half compared to bare LDBCs, and showed a significant shift of the cationic surface charge towards neutrality. Proton nuclear magnetic resonance spectroscopy evidenced twice the total amount of IL on the LDBCs relative to an established IL-linear PLGA platform. Transmission electron microscopy suggested the formation of a nanoparticle surface coating, which acted as a protective agent against RBC hemolysis, reducing hemolysis from 73% (LDBC) to 25% (IL-LDBC). However, dramatically different uptake behavior of IL-LDBCs vs. IL-PLGA NPs in RAW 264.7 macrophage cells suggests a different conformational IL-NP surface assembly on the linear versus the linear-dendritic nanoparticles. These results suggest that by controlling the physical chemistry of polymer-IL interactions and assembly on the nanoscale, biological function can be tailored toward the development of more effective and more precisely targeted therapies.

Lipid Membrane Binding and Cell Protection Efficacy of Poly(1,2-butylene oxide)-b-poly(ethylene oxide) Copolymers.

Poloxamers consisting of poly(ethylene oxide) (PEO) and poly(propylene oxide) segments can protect cell membranes against various forms of stress. We investigated the role of the hydrophobic block chemistry on polymer/membrane binding and cell membrane protection by comparing a series of poly(butylene oxide)-b-PEO (PBO-b-PEO) copolymers to poloxamer analogues, using a combination of pulsed-field-gradient (PFG) NMR experiments and a lactate dehydrogenase (LDH) cell assay. We found that the more hydrophobic PBO-b-PEO copolymers bound more significantly to model liposomes composed of 1-palmitol-2-oleoyl-glycero-3-phosphocholine (POPC) compared to poly(propylene oxide) (PPO)/PEO copolymers. However, both classes of polymers performed similarly when compared by an LDH assay. These results present an important comparison between polymers with similar structures but with different binding affinities. They also provide mechanistic insight as enhanced polymer/lipid membrane binding did not directly translate to increased cell protection in the LDH assay, and therefore, additional factors need to be considered when trying to achieve greater membrane protection efficacy.

Unusual Lower Critical Solution Temperature Phase Behavior of Poly(benzyl methacrylate) in a Pyrrolidinium-Based Ionic Liquid.

Polymer/ionic liquid systems are being increasingly explored, yet those exhibiting lower critical solution temperature (LCST) phase behavior remain poorly understood. Poly(benzyl methacrylate) in certain ionic liquids constitute unusual LCST systems, in that the second virial coefficient (A2) in dilute solutions has recently been shown to be positive, indicative of good solvent behavior, even above phase separation temperatures, where A2 < 0 is expected. In this work, we describe the LCST phase behavior of poly(benzyl methacrylate) in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide for three different molecular weights (32, 63, and 76 kg/mol) in concentrated solutions (5-40% by weight). Turbidimetry measurements reveal a strong concentration dependence to the phase boundaries, yet the molecular weight is shown to have no influence. The critical compositions of these systems are not accessed, and must therefore lie above 40 wt% polymer, far from the values (ca. 10%) anticipated by Flory-Huggins theory. The proximity of the experimental cloud point to the coexistence curve (binodal) and the thermo-reversibility of the phase transitions, are also confirmed at various heating and cooling rates.

Molecular Weight Dependence of Block Copolymer Micelle Fragmentation Kinetics.

The effect of molecular weight (M) on the fragmentation kinetics of micelles formed by 1,2-polybutadiene-block-poly(ethylene oxide) (PB-PEO) copolymers was studied in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. A series of six samples, with total M ranging from 104 to 105 g mol-1 and nearly constant composition (fPEO ≈ 0.4), were examined; all six formed spherical micelles with PEO coronas. Nonequilibrium PB-PEO micelles were prepared by direct dissolution, a process that systematically produces nanoparticles with mean aggregation numbers more than twice the equilibrium values. When subjected to high temperature annealing (170 °C), the average micelle radius was found to decrease substantially, as determined by temperature-jump dynamic light scattering (T-jump DLS) and time-resolved small-angle X-ray scattering (TR-SAXS). The characteristic fragmentation times (τ) were found to increase strongly with increasing degree of polymerization N, as τ ∼ N1.8. This result compares favorably with the prediction of a previously untested model.