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10.1021/acsmacrolett.3c00019

Hydrophobic blocks of amphiphilic block copolymers often form glassy micellar cores at room temperature with a rigid structure that limits their applications as nanocapsules for targeted delivery. Nevertheless, we prepared and analyzed core/shell micelles with a soft core, formed by a self-assembled block copolymer consisting of a hydrophobic block and a polycation block, poly(lauryl acrylate)-block-poly(trimethyl-aminoethyl acrylate) (PLA-QPDMAEA), in aqueous solution. By light and small-angle neutron scattering, by transmission electron microscopy and by fluorescence spectroscopy, we showed that these core/shell micelles are spherical and cylindrical with a fluid-like PLA core and a positively charged outer shell and that they can encapsulate and release hydrophobic solutes. Moreover, after mixing these PLA-QPDMAEA core/shell micelles with another diblock copolymer, consisting of a hydrophilic block and a polyanion block, namely poly(ethylene oxide)-block-poly(methacrylic acid) (PEO-PMAA), we observed the formation of novel vesicle-like multicompartment structures containing both soft hydrophobic and interpolyelectrolyte (IPEC) layers. By combining small-angle neutron scattering with self-consistent field modeling, we confirmed the formation of these complex vesicle-like structures with a swollen PEO core, an IPEC inner layer, a PLA soft layer, an IPEC outer layer and a loose PEO corona. Thus, these multicompartment micelles with fluid and IPEC layers and a hydrophilic corona may be used as nanocapsules with several tunable properties, including the ability to control the thickness of each layer, the charge of the IPEC layers and the stability of the micelles, to deliver both hydrophobic and multivalent solutes.

Lipid nanoparticles (LNPs) are the most clinically advanced delivery system for RNA-based drugs but have predominantly been investigated for intravenous and intramuscular administration. Subcutaneous administration opens the possibility of patient self-administration and hence long-term chronic treatment that could enable messenger RNA (mRNA) to be used as a novel modality for protein replacement or regenerative therapies. In this study, we show that subcutaneous administration of mRNA formulated within LNPs can result in measurable plasma exposure of a secreted protein. However, subcutaneous administration of mRNA formulated within LNPs was observed to be associated with dose-limiting inflammatory responses. To overcome this limitation, we investigated the concept of incorporating aliphatic ester prodrugs of anti-inflammatory steroids within LNPs, i.e., functionalized LNPs to suppress the inflammatory response. We show that the effectiveness of this approach depends on the alkyl chain length of the ester prodrug, which determines its retention at the site of administration. An unexpected additional benefit to this approach is the prolongation observed in the duration of protein expression. Our results demonstrate that subcutaneous administration of mRNA formulated in functionalized LNPs is a viable approach to achieving systemic levels of therapeutic proteins, which has the added benefits of being amenable to self-administration when chronic treatment is required., Graphical abstract, Subcutaneous administration of mRNA formulated within LNPs results in measurable plasma exposure of a secreted protein, albeit with dose-limiting local inflammatory responses. Inclusion of a steroid prodrug in mRNA LNPs resulted in an increased level and duration of protein expression as well as improved tolerability of the LNP following subcutaneous administration.

Metal nanoclusters are a unique class of synthetic material, as their crystal structures can be resolved using X-ray diffraction, and their chemical formula can be precisely determinated from mass spectroscopy. However, a complete structure characterization by these two techniques is often a challenging task. Here, we utilize small-angle neutron scattering (SANS) to directly quantify the key structure parameters of a series of silver and gold nanoclusters in solution. The results not only correlate well to their crystallographic structures, but also allow the quantification of the counterions layer surrounding charged nanoclusters in solution. Furthermore, when combining with X-ray scattering, it is possible to estimate the molecular weight of both the metal core and the ligand shell of nanoclusters. This work offers an alternative characterization tool for nanoclusters without the requirement of crystallization or gas phase ionization.

A fully hydrated Nafion membrane is generally treated as a three-component system comprising the tetrafluoroethylene-like main chain, the fluorinated side chain ending with a sulfonic acid group, and absorbed water. We applied the contrast variation small-angle neutron scattering technique to decompose scattering intensity profiles to partial scattering functions (PSFs) of each component in Nafion quantitatively. In the large scale (>30 nm), structural heterogeneities were observed in the main- and side-chain domains but not in water domains. In the middle scale (5–30 nm), a bicontinuous-like structure of crystalline and amorphous phases with a mean separation distance of 11 nm was observed, as a result of the main-chain semicrystalline templating effect. In the small scale (

Disordered regions as found in intrinsically disordered proteins (IDP) or during protein folding define response time to stimuli and protein folding times. Neutron spin-echo spectroscopy is a powerful tool to directly access the collective motions of the unfolded chain to enlighten the physical origin of basic conformational relaxation. During the thermal unfolding of native ribonuclease A, we examine the structure and dynamics of the disordered state within a two-state transition model using polymer models, including internal friction, to describe the chain dynamics. The presence of four disulfide bonds alters the disordered configuration to a more compact configuration compared to a Gaussian chain that is defined by the additional links, as demonstrated by coarse-grained simulation. The dynamics of the disordered chain is described by Zimm dynamics with internal friction (ZIF) between neighboring amino acids. Relaxation times are dominated by mode-independent internal friction. Internal friction relaxation times show an Arrhenius-like behavior with an activation energy of 33 kJ/mol. The Zimm dynamics is dominated by internal friction and suggest that the characteristic motions correspond to overdamped elastic modes similar to the motions observed for folded proteins but within a pool of disordered configurations spanning the configurational space. For IDP, internal friction dominates while solvent friction and hydrodynamic interactions are smaller corrections.

Conditional variations can lead to micellar transformations resulting in various (equilibrium) morphologies. However, creating differently shaped assemblies under the same final conditions (same ingredients, composition, temperature, etc.) is challenging. We present a thermoresponsive polyelectrolyte system allowing a pathway-dependent preparation of kinetically stable spherical star-like or cylindrical micelles. In more detail, a temperature-induced structure switch is used to generate equilibrated interpolyelectrolyte complex (IPEC) micelles of different morphologies (templates) below and above the lower critical solution temperature in the presence of plasticizer (salt). Then, lowering the salt concentration at a specific temperature kinetically freezes the formed IPECs, keeping the respective microstructural information encoded in the frozen IPEC also at other temperatures. Hence, different nonequilibrium morphologies at the same final conditions are provided. The salt-triggered transition from nonequilibrium to equilibrium micelles can be repeated for the same sample, highlighting a system with an on-demand changeable and restorable structure.

We characterize via small-angle neutron scattering the structural properties of a mixture of all-DNA particles with functionalities 4 (A) and 2 (B) constrained by design to reside close to the percolation threshold. DNA base sequences are selected such that A particles can only bind with B ones and that at the studied temperature (10 °C) all AB bonds are formed and long-lived, originating highly polydisperse persistent equilibrium clusters. The concentration dependence of the scattered intensity and its wavevector dependence is exploited to determine the fractal dimension and the size distribution of the clusters, which are found to be consistent with the critical exponents of the 3-D percolation universality class. The value of DNA nanoparticles as nanometric patchy colloids with well-defined functionality, bonding selectivity, and exquisite control of the interaction strength is demonstrated.

Glucose oxidase (GOx) is a 160 kDa flavoenzyme dimer belonging to the family of glucose-methanol-choline oxidoreductases. Despite the abundant availability of information regarding the structure and mechanisms of interactions of GOx, there is still considerable interest in studying the properties of this protein to extend its bio-applications. The present study aims at investigating the conformational stability of GOx from Aspergillus niger in the optimal environment that presumably preserves its functional properties using small angle neutron scattering method. This method allowed computing the low-resolution three-dimensional models of the protein. Obtained results indicate protein dimerization in buffer solution pH 5.9, with a maximum particle dimension, Dmax, of 110 Å and Rg of 34.50 ± 0.025 Å.

Author(s): Murrey, TL; Hertel, D; Nowak, J; Bruker, R; Limbock, T; Neudorfl, J; Ruth, S; Schelter, J; Olthof, S; Radulescu, A; Moule, AJ; Meerholz, K | Abstract: Merocyanines (MCs) are a versatile class of small-molecule dyes. Their optoelectronic properties are easily tunable by chemically controlling their donor-acceptor strength, and their structural properties can be tuned by simple side-chain substitution. This manuscript demonstrates a novel series of MCs featuring an indoline donor with varying hydrocarbon side-chain length (from 6 to 12 carbons) and a tert-butyl-thiazole acceptor, labeled InTBT. Bulk heterojunction organic photovoltaics are fabricated with a [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) acceptor and characterized. Films composed of I8TBT:PCBM and I9TBT:PCBM produced the highest power conversion efficiency of 4.5%, which suggests that the morphology is optimized by controlling the side-chain length. Hierarchical structure formation in InTBT:PCBM films is studied using grazing incidence X-ray diffraction (GIXRD), small-angle neutron scattering (SANS), and atomic force microscopy (AFM). When mixed with PCBM, InTBTs with ≤8 side-chain carbons form pure crystalline domains, while InTBTs with ≥9 side-chain carbons mix well with PCBM. SANS demonstrates that increasing side-chain length increases the InTBT-rich domain size. In addition, a branched hexyl-dodecyl side-chain IHDTBT:PCBM film was studied and found to exhibit the worst-performance organic photovoltaic (OPV) device. The large-branched side chain inhibited mixing between IHDTBT and PCBM resulting in large segregated phases.

The use of technologies based on soft polymer particles represents an effective way to deliver target molecules with a specific function. To design a well-performing delivery system, it is fundamental to rationalize both the aggregation and the structural properties of such particles. In this study, we present the kinetic and structural characterization over time of poly(vinyl alcohol) (PVA) microgels obtained through a salting-out process in the presence of NaCl. We have analyzed how both the polymer and salt concentrations affect the aggregation process. The aggregation rate as well as the morphology and physico-chemical parameters, such as mass and chain density of the microgels, have been determined through static and dynamic light scattering and discussed in the framework of the diffusion-limited and reaction-limited colloid aggregation. Insights into the polymer chain arrangements and their dynamics have been gained by means of small-angle neutron scattering and neutron spin-echo measurements. As a result, it was found that NaCl induces a liquid phase separation in solution with the formation of spherical PVA microaggregates, which grow under a reaction-limited aggregation mechanism. The particles increase their size and compactness over time. Within the aggregate, the polymer chains are locally organized to form randomly oriented lamellae with a thickness of about 60 Å. The internal dynamics is a complex mixture of diffusion, Zimm dynamics, and possibly effects from crowding with the transition to a Rouse-like behavior. The microparticle preparation based on the salting-out process constitutes a novelty, if compared to the methods already existing and based on the use of chemical cross-linkers, and is a cheap and easy protocol that allows tuning both particle size and density by varying the salt concentration.

International journal of molecular sciences 23(13), 6969 (2022). doi:10.3390/ijms23136969 special issue: "Special Issue "Probing Protein Conformational Plasticity" / Special Issue Editor: Dr. Andreas Stadler, Guest Editor", Published by Molecular Diversity Preservation International, Basel

Amphiphilic gradient copolymers represent a promising alternative to extensively used block copolymers due to their facile one-step synthesis by statistical copolymerization of monomers of different reactivity. Herein, an in-depth analysis is provided of micelles based on amphiphilic gradient poly(2-oxazoline)s with different chain lengths to evaluate their potential for micellar drug delivery systems and compare them to the analogous diblock copolymer micelles. Size, morphology, and stability of self-assembled nanoparticles, loading of hydrophobic drug curcumin, as well as cytotoxicities of the prepared nanoformulations are examined using copoly(2-oxazoline)s with varying chain lengths and comonomer ratios. In addition to several interesting differences between the two copolymer architecture classes, such as more compact self-assembled structures with faster exchange dynamics for the gradient copolymers, it is concluded that gradient copolymers provide stable curcumin nanoformulations with comparable drug loadings to block copolymer systems and benefit from more straightforward copolymer synthesis. The study demonstrates the potential of amphiphilic gradient copolymers as a versatile platform for the synthesis of new polymer therapeutics. acceptedVersion

The small-angle neutron scattering (SANS) on HeLa nuclei demonstrates the bifractal nature of the chromatin structural organization. The border line between two fractal structures is detected as a crossover point at ${Q}_{c}\ensuremath{\approx}4\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}2}\phantom{\rule{4pt}{0ex}}{\mathrm{nm}}^{\ensuremath{-}1}$ in the momentum transfer dependence ${Q}^{\ensuremath{-}D}$. The use of contrast variation (${\mathrm{D}}_{2}\mathrm{O}\text{\ensuremath{-}}{\mathrm{H}}_{2}\mathrm{O}$) in SANS measurements reveals clear similarity in the large scale structural organizations of nucleic acids (NA) and proteins. Both NA and protein structures have a mass fractal arrangement with the fractal dimension of $D\ensuremath{\approx}2.5$ at scales smaller than 150 nm down to 20 nm. Both NA and proteins show a logarithmic fractal behavior with $D\ensuremath{\approx}3$ at scales larger than 150 nm up to 6000 nm. The combined analysis of the SANS and atomic force microscopy data allows one to conclude that chromatin and its constitutes (DNA and proteins) are characterized as soft, densely packed, logarithmic fractals on the large scale and as rigid, loosely packed, mass fractals on the smaller scale. The comparison of the partial cross sections from NA and proteins with one from chromatin as a whole demonstrates spatial correlation of two chromatin's components in the range up to 900 nm. Thus chromatin in HeLa nuclei is built as the unified structure of the NA and proteins entwined through each other. Correlation between two components is lost upon scale increases toward 6000 nm. The structural features at the large scale, probably, provide nuclei with the flexibility and chromatin-free space to build supercorrelations on the distance of ${10}^{3}$ nm resembling cycle cell activity, such as an appearance of nucleoli and a DNA replication.

Low permeability of the urinary bladder epithelium, poor retention of the chemotherapeutic agents due to dilution and periodic urine voiding as well as intermittent catheterisations are the major limitations of intravesical drug delivery used in the treatment of bladder cancer. In this work, maleimide-functionalised poly(lactide-co-glycolide)-block-poly(ethylene glycol) (PLGA-PEG-Mal) nanoparticles were developed. Their physicochemical characteristics, including morphology, architecture and molecular parameters have been investigated by means of dynamic light scattering, transmission electron microscopy and small-angle neutron scattering techniques. It was established that the size of nanoparticles was dependent on the solvent used in their preparation and molecular weight of PEG, for example, 105 ± 1 nm and 68 ± 1 nm particles were formed from PLGA20K-PEG5K in dimethyl sulfoxide and acetone, respectively. PLGA-PEG-Mal nanoparticles were explored as mucoadhesive formulations for drug delivery to the urinary bladder. The retention of fluorescein-loaded nanoparticles on freshly excised lamb bladder mucosa in vitro was evaluated and assessed using a flow-through fluorescence technique and Wash Out50 (WO50) quantitative method. PLGA-PEG-Mal nanoparticles (NPs) exhibited greater retention on urinary bladder mucosa (WO50 = 15 mL) compared to maleimide-free NPs (WO50 = 5 mL). The assessment of the biocompatibility of PEG-Mal using the slug mucosal irritation test revealed that these materials are non-irritant to mucosal surfaces.

The properties of ligand protected gold nanoparticles are determined by the synergistic interplay of their structural components, including the metal core, the ligand shell, and the solvation layer. However, the simultaneous characterization of all these components remains a major challenge given their disparate chemical nature. In the case of mixed ligand nanoparticles, this task becomes daunting due to the presence of intercorrelated additional parameters such as the ligand ratio, ligand spatial distribution, and solvation of the heterogeneous ligand shell. Here we show that small angle neutron scattering (SANS) is a tool capable of simultaneously characterizing the core and the ligand shell of monodisperse mixed ligand gold nanoparticles. We systematically examine how each parameter (e.g., the core size, the thickness, composition and the spatial heterogeneity of the ligand shell) affects nanoparticles' scattering profile. Quantitative information on these parameters is retrieved using analytical fitting as well as 3D modeling. Importantly, we show that SANS can evaluate the solvation degree of mixed ligand protected gold nanoparticles, a challenging task for any other characterization methods.

We studied anion transport behaviors in grafted anion exchange membranes (AEMs) composed of 2-methyl-N-vinylimidazole (Im) and styrene (St) having various Im/St ratios (6/4, 4/6, and 3/7) grafted onto poly(ethylene-co-tetrafluoroethylene) films (named AEM64, AEM46, and AEM37). The transport properties were evaluated based on the transport efficiency defined as ratios of anion diffusion coefficients in AEMs to dilution solutions (D/D0) and were correlated to the morphology of AEMs analyzed by the small angle scattering method. We found a master curve of D/D0 with hydration for AEM64, regardless of the grafting degree and anion species; however, D/D0 for AEM46 and AEM37 was similar with AEM64 at low hydration conditions, but clearly deviated down from it at high hydration conditions. Such difference could be elucidated by the membrane morphology. For AEM64, the conducting phase was homogeneous comprised dispersed ions, and the conductivity correlated well with the increasing hydration. In contrast, when the styrene content increased (i.e., AEM46 and AEM37), the conducting phase changed to heterogeneous with water puddles separated from dispersed ions, and the anion transport was suppressed. Results in this work gave a mechanistic insight in the anion transport properties in proximity of the AEM morphology at various hydration conditions.

The preparation of poly(N-isopropylacrylamide) microgels via classical precipitation polymerization (batch method) and a continuous monomer feeding approach (feeding method) leads to different internal crosslinker distributions, i.e., from core–shell-like to a more homogeneous one. The internal structure and dynamics of these microgels with low and medium crosslinker concentrations are studied with dynamic light scattering and small-angle neutron scattering in a wide q-range below and above the volume phase transition temperature. The influence of the preparation method, and crosslinker and initiator concentration on the internal structure of the microgels is investigated. In contrast to the classical conception where polymer microgels possess a core–shell structure with the averaged internal polymer density distribution within the core part, a detailed view of the internal inhomogeneities of the PNIPAM microgels and the presence of internal domains even above the volume phase transition temperature, when polymer microgels are in the deswollen state, are presented. The correlation between initiator concentration and the size of internal domains that appear inside the microgel with temperature increase is demonstrated. Moreover, the influence of internal inhomogeneities on the dynamics of the batch- and feeding-microgels studied with neutron spin-echo spectroscopy is reported.

Two imidazolium based graft-type of anion-conducting electrolyte membranes (AEMs) for fuel cells with a moderate ion exchange capacity of ∼1.0 mmol/g were successfully prepared by radiation-induced grafting to introduce imidazolium and styrene units into a poly(ethylene-co-tetrafluoroethylene) (ETFE) base film. Though imidazolium groups were desired to connect with styrene groups via two different ways, i.e. parallel or perpendicular orientations to the graft-polymer chains via copolymerization (AEM1) or homo-polymerization (AEM2), both AEMs possess high ion conductivity (>100 mS/cm at 60 °C) and modest stability. The morphologies of these membranes were elucidated by small-angle neutron scattering method. Our results revealed that 1) both AEMs show clear microphase separation with a length scale of 30–40 nm, and the semi-crystalline structural feature of the hydrophobic microdomains contributes to the membrane mechanical property; 2) at the length scale

Extracellular polysaccharides are widely produced by bacteria, yeasts, and algae. These polymers are involved in several biological functions, such as bacteria adhesion to surface and biofilm formation, ion sequestering, protection from desiccation, and cryoprotection. The chemical characterization of these polymers is the starting point for obtaining relationships between their structures and their various functions. While this fundamental correlation is well reported and studied for the proteins, for the polysaccharides, this relationship is less intuitive. In this paper, we elucidate the chemical structure and conformational studies of a mannan exopolysaccharide from the permafrost isolated bacterium Psychrobacter arcticus strain 273-4. The mannan from the cold-adapted bacterium was compared with its dephosphorylated derivative and the commercial product from Saccharomyces cerevisiae. Starting from the chemical structure, we explored a new approach to deepen the study of the structure/activity relationship. A pool of physicochemical techniques, ranging from small-angle neutron scattering (SANS) and dynamic and static light scattering (DLS and SLS, respectively) to circular dichroism (CD) and cryo-transmission electron microscopy (cryo-TEM), have been used. Finally, the ice recrystallization inhibition activity of the polysaccharides was explored. The experimental evidence suggests that the mannan exopolysaccharide from P. arcticus bacterium has an efficient interaction with the water molecules, and it is structurally characterized by rigid-rod regions assuming a 14-helix-type conformation.

We recently developed a simultaneous measurement system combining a wide Q-range SANS instrument and a Fourier-transform infrared (FTIR) spectrometer equipped with an infrared polarizer. The information of high Q neutron scattering and FTIR spectra helps to increase the reliability of structural analysis by SANS on complicated systems. In this study, we applied this simultaneous measurement system to a cocrystal system of syndiotactic polystyrene (sPS) and methyl benzoate (MeBA). The neutron scattering provided the evidence that MeBA molecules were certainly incorporated into the crystalline region of sPS. The polarized FTIR measurements showed that the guest MeBA has a certain orientation against the sPS lattice. With the help of different kinds of structure information, the thermal behavior of sPS/MeBA cocrystal was able to be analyzed in detail.

The combination of polymeric surfactants with different features into mixed micelles give access to properties that may be superior to the single-component micelles. In this work, we investigated synergistic effects in mixtures of D-α-Tocopheryl polyethylene glycol succinate (TPGS) with poloxamines (also known as Tetronic), pH-responsive and thermogelling polyethylene oxide (PEO)-polypropylene oxide (PPO) 4-arm block copolymers. We examined the morphology of the self-assembled micelles of TPGS with Tetronic 1107 (T1107) and 908 (T908) in the presence of naproxen (NA), used as a model drug, and assessed the capacity of the single and mixed micelles to trap the guest, using a combination of small-angle neutron scattering (SANS) and NMR spectroscopy (1D, 2D-NOESY and diffusion NMR), over a range of compositions and temperatures, in the dilute regime and gel state. NA did not interact with T1107 or T908 in their unimer form, but it was incorporated into the hydrophobic core of the micelles above the critical micellar temperature (CMT). In contrast, TPGS dissolved NA at any temperature, mainly in the tocopherol core, with some partitioning in the PEG-shell. The micellar structure was not altered by the presence of NA, except for an expansion of the core size, a result of the preferential accumulation of NA in that compartment. The solubility of the drug in single component micelles increased markedly with temperature, while mixed micelles produced an intermediate enhancement of the solubility between that of TPGS and the poloxamines, which increased at higher TPGS/poloxamine ratios. Micellar hydrogels formed by the packing of the polymeric mixed micelles in a BCC macrolattice, whose structure was not altered by the presence of the drug (at least at 0.2 wt%). The applicability of the drug-loaded gels for topical formulations was explored by transdermal diffusion testing using a synthetic model of skin, showing that the diffusion of NA across the membrane was enhanced by incorporating small amounts of TPGS to the hydrogel, especially with the more hydrophilic T908.

The bacterial cytoplasmic membrane is the innermost bacterial membrane and is mainly composed of three different phospholipid species, i.e., phosphoethanolamine (PE), phosphoglycerol (PG), and cardiolipin (CL). In particular, PG and CL are responsible for the negative charge of the membrane and are often the targets of cationic antimicrobial agents. The growing resistance of bacteria toward the available antibiotics requires the development of new and more efficient antibacterial drugs. In this context, studying the physicochemical properties of the bacterial cytoplasmic membrane is pivotal for understanding drug-membrane interactions at the molecular level as well as for designing drug-testing platforms. Here, we discuss the preparation and characterization of PE/PG/CL vesicle suspensions, which contain all of the main lipid components of the bacterial cytoplasmic membrane. The vesicle suspensions were characterized by means of small-angle neutron scattering, dynamic light scattering, and electron paramagnetic spectroscopy. By combining solution scattering and spectroscopy techniques, we propose a detailed description of the impact of different CL concentrations on the structure and dynamics of the PE/PG bilayer. CL induces the formation of thicker bilayers, which exhibit higher curvature and are overall more fluid. The experimental results contribute to shed light on the structure and dynamics of relevant model systems of the bacterial cytoplasmic membrane.

Hypothesis The combination of polymeric surfactants into mixed micelles is expected to improve properties relevant to their use in drug delivery, such as micellar size, gelation, and toxicity. We investigated synergistic effects in mixtures of D-α-Tocopheryl polyethylene glycol succinate (TPGS), an FDA-approved PEGylated derivative of vitamin E, and Tetronic surfactants, pH-responsive and thermogelling polyethylene oxide (PEO)-polypropylene oxide (PPO) 4-arm block copolymers. We hypothesized that mixed micelles would form under specific conditions and provide a handle to tune formulation characteristics. Experiments We examined the morphology of the self-assembled structures in mixtures of TPGS with two Tetronic: T1107 and T908, using a combination of dynamic light scattering (DLS), small-angle neutron scattering (SANS), NMR spectroscopy (NOESY and diffusion NMR) and oscillatory rheology, over a range of compositions, temperatures and pH. Cell viability was assessed in NIH/3T3 fibroblasts. Findings The combination of TPGS with either of the two Tetronic produces spherical core-shell micelles that comprise both surfactants in their structure (mixed micelles). T1107 unimers incorporate into TPGS aggregates below the critical micelle temperature of the poloxamine, while mixed micelles only form under limited conditions with T908. At high concentration/temperature, small proportions of TPGS extend the gel phase, more markedly with T1107, with similar elastic moduli (30–50 kPa) and a BCC crystalline structure. Cell viability of NIH/3T3 fibroblasts grown in the hydrogels increases significantly when the poloxamine gels are doped with TPGS, making the combination of poloxamines and TPGS a promising platform for drug delivery.

The β-hydrogen-free imidazole monomer, 2-methyl-N-methyl-4(5)-vinylimidazole (2M4VIm), is synthesized to prepare anion exchange membranes (AEMs). The radiation-induced graft polymerization of 2M4VIm and styrene is performed in poly(ethylene-co-tetrafluoroethylene), followed by N-alkylation and ion exchange reactions to prepare 4-vinylimidazolium-containing AEM (2M4VIm/St-AEM). AEMs that have a 6/4 2M4VIm/St molar ratio and 1.7 mmol g−1 ion exchange capacity (IEC) result in 75 mS cm−1 conductivity and 60% water uptake at room temperature in water, demonstrating enhanced values compared to previously reported 2-methyl-N-vinylimidazolium-containing AEMs (2MNVIm/St-AEM) that have a similar comonomer ratio and IEC. The small-angle neutron scattering measurements of dry and swollen 2M4VIm/St-AEM reveal hydrophilic/hydrophobic two-phase separation, as observed for 2MNVIm/St-AEM with a similar Im/St composition. 2M4VIm/St-AEMs exhibit higher alkaline stability in 1 m KOH at 80 °C at an early stage owing to the suppression of imidazolium β-elimination but lower long-term stability than that of 2MNVIm/St-AEM due to the ring-opening reaction of the imidazolium group due to its outward orientation from the graft main chain.