61 research outputs found
Biopolymers, nanoparticles and surfactants: short stories in building-up gels from self- assembly
Hydrogels obtained from the chemical and physical association of macromolecules, surfactants and nanoparticles, are a huge area of materials science and have found numerous applications in food, personal care products and biomedicine. The macroscopic properties of hydrogels are a complex interplay between the microscopic and mesoscopic supramolecular organization; thus, both their dynamics and structure are dictated by the interactions between the constituents, the fabrication pathway and resulting spatial organization over different length scales. Work in our group has explored various approaches to make gels from non-covalent interactions, spanning biopolymers1-4, wormlike micelles5,6 or host-guest interactions with cyclodextrins7-9.
Biopolymers offer a number of advantages over their synthetic counterparts, but suffer from a lack of characterization. This talk will describe our approach to make cheap, functional materials based on widely available biopolymers obtained from natural sources, such as gelatin, or polysaccharides.1-4,10 We will describe the impact of using a hybrid gelation process, combining physical gelling and chemical cross-linking, as well as gels made from hydrophobic interactions between modified biopolymers (dextran or gellan gum) with surfactant micelles.10 Time allowing, I will report on some recent work involving surfactants and laponite architectures, leading to pH- and temperature-responsive gels. The nanoscale morphology of these gels is characterized by small-angle neutron scattering, which is correlated to the rheology of the gels to extract useful structure-function relationships.
[1] M.A. da Silva et al. Biomacromolecules (2015) 16, 1401-1409
[2] M.A. da Silva et al. Macromolecular Bioscience (2014) 14, 817-830.
[3] F. Bode et al. Soft Matter (2013) 9, 6986-6999
[4] F. Bode et al. Biomacromolecules (2011) 12, 3741-3752
[5] C. A. Dreiss Soft Matter (2007) 2, 956-970
[6] C. Zonglin et al. Chem. Soc. Rev. (2013) 42, 7174-7203
[7] G. GonzĂĄlez-Gaitano et al. Langmuir (2015) 31, 5645-5655
[8] A.G. Peréz et al. Langmuir (2014) 30, 11552-11562
[9] M.A. da Silva et al. Langmuir (2013) 29, 7697-7708
[10] H. Afifi et al. Soft Matter (2011) 7, 4888-489
Dynamic covalent surfactants and their uses in the development of smart materials
Dynamic covalent chemistry, which leverages the dynamic nature of reversible covalent bonds controlled by the conditions of reaction equilibrium, has demonstrated great potential in diverse applications related to both the stability of covalent bonds and the possibility of exchanging building blocks, imparting to the systems the possibility of âerror checkingâ and âproof-readingâ. By incorporating dynamic covalent bonds into surfactant molecular architectures, combinatorial libraries of surfactants with bespoke functionalities can be readily fabricated through a facile strategy, with minimum effort in organic synthesis. Consequently, a multidisciplinary field of research involving the creation and application of dynamic covalent surfactants has recently emerged, which has aroused great attention in surfactant and colloid science, supramolecular chemistry, self-assembly, smart materials, drug delivery, and nanotechnology. This review reports results in this field published over recent years, discusses the possibilities presented by dynamic covalent surfactants and their applications in developing smart self-assembled materials, and outlines some future perspectives
Characterisation of the Prion Protein Oligomerisation by Md Simulations and Small Angle X-Ray Scattering
StimuliâResponsive Polymers for Engineered Emulsions
© 2024 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH. This is an open access article distributed under the terms of the Creative Commons Attribution License (CC BY), https://creativecommons.org/licenses/by/4.0/Emulsions are complex. Dispersing two immiscible phases, thus expanding an interface, requires effort to achieve and the resultant dispersion is thermodynamically unstable, driving the system toward coalescence. Furthermore, physical instabilities, including creaming, arise due to presence of dispersed droplets of different densities to a continuous phase. Emulsions allow the formulation of oils, can act as vehicles to solubilize both hydrophilic and lipophilic molecules, and can be tailored to desirable rheological profiles, including âgelâlikeâ behavior and shear thinning. The usefulness of emulsions can be further expanded by imparting stimuliâresponsive or âsmartâ behaviors by inclusion of a stimuliâresponsive emulsifier, polymer or surfactant. This enables manipulation like gelation, breaking, or aggregation, by external triggers such as pH, temperature, or salt concentration changes. This platform generates functional materials for pharmaceuticals, cosmetics, oil recovery, and colloid engineering, combining both smart behaviors and intrinsic benefit of emulsions. However, with increased functionality comes greater complexity. This review focuses on the use of stimuliâresponsive polymers for the generation of smart emulsions, motivated by the great adaptability of polymers for this application and their efficacy as steric stabilizers. Stimuliâresponsive emulsions are described according to the trigger used to provide the reader with an overview of progress in this field.Peer reviewe
Polymer architecture dictates thermoreversible gelation in engineered emulsions stabilised with branched copolymer surfactants
© The Royal Society of Chemistry 2022. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.The generation of materials that switch from a liquid to gel state upon warming can enable new healthcare technologies with improved functionality, such as in situ gel-forming materials for drug delivery to topical or parenteral sites. The majority of these materials are aqueous polymer solutions, which then suffer from an inability to solubilise hydrophobic drugs. This study investigates the generation of thermoresponsive âengineered emulsionsâ which are low-viscosity emulsions at low temperature and switch to a gel state upon warming. This is achieved by the synthesis of novel branched copolymer surfactants (BCS) containing di(ethylene glycol) methyl ether methacrylate (DEGMA) as a thermoresponsive component giving a lower critical solution temperature (LCST). The copolymers were employed as emulsifiers to prepare 1â:â1 dodecane:water emulsion systems. The effect of polymer architecture is shown to be intimately linked to the rheology of these systems, where branching, elevation of molecular weight, and the presence of hydrophobic end groups is demonstrated to be commensurate with gel formation upon heating. Mechanisms of gel formation were probed by small-angle neutron scattering, which demonstrated that the branched copolymer surfactants formed oblate ellipsoids in solution that grew anisotropically with temperature, forming larger disk-like nanoparticles. The formation of these elongated particles leads to thickening of the emulsions, whilst connectivity of the aggregates and BCS at the oilâwater interface is required for gel formation to occur. Overall, the study provides design principles for this novel class of thermoresponsive material with great potential in healthcare, cosmetic, and energy applications.Peer reviewe
On the absolute calibration of bench-top small-angle X-ray scattering instruments: a comparison of different standard methods
Combining branched copolymers with additives generates stable thermoresponsive emulsions with in situ gelation upon exposure to body temperature
© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).Branched copolymer surfactants (BCS) containing thermoresponsive polymer components, hydrophilic components, and hydrophobic termini allow the formation of emulsions which switch from liquid at room temperature to a gel state upon heating. These materials have great potential as in situ gel-forming dosage forms for administration to external and internal body sites, where the emulsion system also allows effective solubilisation of a range of drugs with different chemistries. These systems have been reported previously, however there are many challenges to translation into pharmaceutical excipients. To transition towards this application, this manuscript describes the evaluation of a range of pharmaceutically-relevant oils in the BCS system as well as evaluation of surfactants and polymeric/oligomeric additives to enhance stability. Key endpoints for this study are macroscopic stability of the emulsions and rheological response to temperature. The effect of an optimal additive (methylcellulose) on the nanoscale processes occurring in the BCS-stabilised emulsions is probed by small-angle neutron scattering (SANS) to better comprehend the system. Overall, the study reports an optimal BCS/methylcellulose system exhibiting solâgel transition at a physiologically-relevant temperature without macroscopic evidence of instability as an in situ gelling dosage form.Peer reviewe
Thermoresponsive TriblockâCopolymers of Polyethylene Oxide and Polymethacrylates: Linking Chemistry, Nanoscale Morphology, and Rheological Properties
© 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, https://creativecommons.org/licenses/by/4.0/Abstract: Thermoreversible gels switch from a freeâflowing liquid state to an elastic gel mesophase upon warming, displaying the reverse transition upon cooling. While this phenomenon makes these advanced materials highly attractive in numerous fields, the generation of optimal materials of tailored rheology and transition temperatures is stifled by the lack of design principles. To address this need, a library of ABA copolymers has been prepared with âAâ blocks exhibiting thermoresponsive behavior and âBâ blocks of poly(ethylene glycol). This library evaluates the effect of âAâ chemistry, probing three polymer classes, and A/B block molecular weight on thermallyâinduced phase changes in solutions of the polymers. An exploration by rheometry coupled to SmallâAngle Neutron Scattering (SANS) elucidates temperatureâdependent hierarchical selfâassembly processes occurring on the nanoscale as well as bulk rheology. This process deciphered links between rheology and supracolloidal assemblies (sphere, ellipses, and cylinders) within the gel state with interactions probed further via structure factors. Several design principles are identified to inform the genesis of nextâgeneration thermoreversible gels, alongside novel materials exhibited thermoresponsive behavior in the solution state for use in applied healthcare technologies.Peer reviewedFinal Published versio
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Supramolecular hybrid structures and gels from hostâguest interactions between α-cyclodextrin and PEGylated organosilica nanoparticles
Polypseudorotaxanes are polymer chains threaded by molecular rings that are free to unthread; these âpearl-necklaceâ can self-assemble further, leading to higher-order supramolecular structures with interesting functionalities. In this work, the complexation between α-cyclodextrin (α-CD), a cyclic oligosaccharide of glucopyranose units, and poly(ethylene glycol) (PEG) grafted to silica nanoparticles was studied. The threading of α-CD onto the polymeric chains leads to their aggregation into bundles, followed by either the precipitation of the inclusion complex or the formation of a gel phase, in which silica nanoparticles are incorporated. The kinetics of threading, followed by turbidimetry, revealed a dependence of the rate of complexation on the following parameters: the concentration of α-CD, temperature, PEG length (750, 4000, and 5000 g molâ1), whether the polymer is grafted or free in solution, and the density of grafting. Complexation is slower, and temperature has a higher impact on PEG grafted on silica nanoparticles compared to PEG free in solution. Thermodynamic parameters extracted from the transition-state theory showed that inclusion complex formation is favored with grafted PEG compared to free PEG and establishes a ratio of complexation of five to six ethylene oxide units per cyclodextrin. The complexation yields, determined by gravimetry, revealed that much higher yields are obtained with longer chains and higher grafting density. Thermogravimetric analysis and Fourier transform infrared spectroscopy on the inclusion complex corroborate the number of macrocycles threaded on the chains. A solâgel transition was observed with the longer PEG chain (5k) at specific mixing ratios; oscillatory shear rheology measurements confirmed a highly solid-like behavior, with an elastic modulus GâČ of up to 25 kPa, higher than that in the absence of silica. These results thus provide the key parameters dictating inclusion complex formation between cyclodextrin and PEG covalently attached to colloidal silica and demonstrate a facile route toward soft nanoparticle gels based on hostâguest interactions
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