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Understanding structure-property relationships is critical for the development of new drug delivery systems. This study investigates the properties of Pluronic smart hydrogel ...formulations for future use as injectable controlled drug carriers. The smart hydrogels promise to enhance patient compliance, decrease side effects and reduce dose and frequency. Pharmaceutically, these systems are attractive due to their unique sol-gel phase transition in the body, biocompatibility, safety and injectability as solutions before transforming into gel matrices at body temperature. We quantify the structural changes of F127 systems under controlled temperature after flow, as experienced during real bodily injection. Empirical formulae combining the coupled thermal and shear dependency are produced to aid future application of these systems. Induced structural transitions measured in-situ by small angle x-ray and neutron scattering reveal mixed oriented structures that can be exploited to tailor the drug release profile.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Semipermeable polymeric anion exchange membranes are essential for separation, filtration and energy conversion technologies including reverse electrodialysis systems that produce energy from ...salinity gradients, fuel cells to generate electrical power from the electrochemical reaction between hydrogen and oxygen, and water electrolyser systems that provide H
fuel. Anion exchange membrane fuel cells and anion exchange membrane water electrolysers rely on the membrane to transport OH
ions between the cathode and anode in a process that involves cooperative interactions with H
O molecules and polymer dynamics. Understanding and controlling the interactions between the relaxation and diffusional processes pose a main scientific and critical membrane design challenge. Here quasi-elastic neutron scattering is applied over a wide range of timescales (10
-10
ps) to disentangle the water, polymer relaxation and OH
diffusional dynamics in commercially available anion exchange membranes (Fumatech FAD-55) designed for selective anion transport across different technology platforms, using the concept of serial decoupling of relaxation and diffusional processes to analyse the data. Preliminary data are also reported for a laboratory-prepared anion exchange membrane especially designed for fuel cell applications.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Oil-in-water emulsions have been stabilized by functionalized cellulose nanofibrils bearing either a negative (oxidized cellulose nanofibrils, OCNF) or a positive (cationic cellulose nanofibrils, ...CCNF) surface charge. The size of the droplets was measured by laser diffraction, while the structure of the shell of the Pickering emulsion droplets was probed using small-angle neutron scattering (SANS), confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM), and rheology measurements. Both OCNF- and CCNF-stabilized emulsions present a very thick shell (>100 nm) comprised of densely packed CNF. OCNF-stabilized emulsions proved to be salt responsive, influencing the droplet aggregation and ultimately the gel properties of the emulsions, while CCNF emulsions, on the other hand, showed very little salt-dependent behavior.
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IJS, KILJ, NUK, PNG, UL, UM
Creams are multi-component semi-solid emulsions that find widespread utility across a wide range of pharmaceutical, cosmetic, and personal care products, and they also feature prominently in ...veterinary preparations and processed foodstuffs. The internal architectures of these systems, however, have to date been inferred largely through macroscopic and/or indirect experimental observations and so they are not well-characterized at the molecular level. Moreover, while their long-term stability and shelf-life, and their aesthetics and functional utility are critically dependent upon their molecular structure, there is no real understanding yet of the structural mechanisms that underlie the potential destabilizing effects of additives like drugs, anti-oxidants or preservatives, and no structure-based rationale to guide product formulation. In the research reported here we sought to address these deficiencies, making particular use of small-angle neutron scattering and exploiting the device of H/D contrast variation, with complementary studies also performed using bright-field and polarised light microscopy, small-angle and wide-angle X-ray scattering, and steady-state shear rheology measurements. Through the convolved findings from these studies we have secured a finely detailed picture of the molecular structure of creams based on Aqueous Cream BP, and our findings reveal that the structure is quite different from the generic picture of cream structure that is widely accepted and reproduced in textbooks.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Fibrous networks constructed from high aspect ratio protein building blocks are ubiquitous in nature. Despite this ubiquity, the functional advantage of such building blocks over globular proteins is ...not understood. To answer this question, we engineered hydrogel network building blocks with varying numbers of protein L domains to control the aspect ratio. The mechanical and structural properties of photochemically crosslinked protein L networks were then characterised using shear rheology and small angle neutron scattering. We show that aspect ratio is a crucial property that defines network architecture and mechanics, by shifting the formation from translationally diffusion dominated to rotationally diffusion dominated. Additionally, we demonstrate that a similar transition is observed in the model living system: fibrin blood clot networks. The functional advantages of this transition are increased mechanical strength and the rapid assembly of homogenous networks above a critical protein concentration, crucial for in vivo biological processes such as blood clotting. In addition, manipulating aspect ratio also provides a parameter in the design of future bio-mimetic and bio-inspired materials.
Investigating proteins with techniques such as NMR or neutron scattering frequently requires the partial or complete substitution of D2O for H2O as a solvent, often tacitly assuming that such a ...solvent substitution does not significantly alter the properties of the protein. Here, we report a systematic investigation of the solvent isotope effect on the phase diagram of the lens protein γB-crystallin in aqueous solution as a model system exhibiting liquid–liquid phase separation. We demonstrate that the observed strong variation of the critical temperature T c can be described by the extended law of corresponding states for all H2O/D2O ratios, where scaling of the temperature by T c or the reduced second virial coefficient accurately reproduces the binodal, spinodal, and osmotic compressibility. These findings highlight the impact of H2O/D2O substitution on γB-crystallin properties and warrant further investigations into the universality of this phenomenon and its underlying mechanisms.
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IJS, KILJ, NUK, PNG, UL, UM
It has been found that the thermoresponsive behavior of emulsions stabilized by block copolymer surfactants (BCSs) can induce either gelation or emulsion break‐up with mild temperature changes. A ...hydrophilic, steric‐stabilizing component of the BCS, polyethylene glycol methacrylate (PEGMA), is crucial to control the thermoresponsive behavior of the emulsions: longer PEG chains (950 g mol−1) lead to thermoregulation, whereas shorter PEGM chains (500 or 300 g mol−1) lead to emulsion break‐up upon mild heating. Additionally, the relative abundance of PEGMA to the thermoresponsive component in the BCS controls the gelation temperature of BCS‐stabilized emulsions. Small‐angle neutron scattering and transmission electron microscopy reveal that the BCS forms oblate ellipsoids which grow anisotropically with temperature. In samples that form a gel, there is evidence that these nano‐objects form supra‐colloidal structures, which are responsible for the gel mesophase formation. An optimal BCS can form emulsions that transition from a liquid to gel state when warmed above 32 °C. This makes the system ideal for in situ gelation upon contact with the body. Overall, this study highlights the great potential of BCSs in generating thermoresponsive emulsions for drug delivery and other healthcare applications.
Stimuli‐responsive emulsions stabilized by branched copolymers have been shown to exhibit either temperature‐induced gelation or breaking by control of polymer architecture. Reducing the molecular weight of a hydrophilic stabilizer block favors temperature‐induced breaking, whilst the relative abundance of this component can control transition temperatures to allow a sol‐gel switch when heated to body temperature.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
It is well-established that oil-in-water creams can be stabilised through the formation of lamellar liquid crystal structures in the continuous phase, achieved by adding (emulsifier) mixtures ...comprising surfactant(s) combined (of necessity) with one or more co-surfactants. There is little molecular-level understanding, however, of how the microstructure of a cream is modulated by changes in co-surfactant and of the ramifications of such changes on cream properties. We investigate here the molecular architectures of oil-free, ternary formulations of water and emulsifiers comprising sodium dodecyl sulfate and one or both of the co-surfactants hexadecanol and octadecanol, using microscopy, small-angle and wide-angle X-ray scattering and small-angle neutron scattering. We then deploy these techniques to determine how the structures of the systems change when liquid paraffin oil is added to convert them to creams, and establish how the structure, rheology, and stability of the creams is modified by changing the co-surfactant. The ternary systems and their corresponding creams are shown to contain co-surfactant lamellae that are subtly different and exhibit different thermotropic behaviours. The lamellae within the creams and the layers surrounding their oil droplets are shown to vary with co-surfactant chain length. Those containing a single fatty alcohol co-surfactant are found to contain crystallites, and by comparison with the cream containing both alcohols suffer adverse changes in their rheology and stability.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Abstract
We explore the use of rheo-small-angle neutron scattering as a method to collect structural information from neutron scattering simultaneously with rheology to understand how ...low-molecular-weight hydrogels form and behave under shear. We examine three different gelling hydrogel systems to assess what structures are formed and how these influence the rheology. Furthermore, we probe what is happening to the network during syneresis and why the gels do not recover after an applied strain. All this information is vital when considering gels for applications such as 3D-printing and injection.
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