Nanostructure in Amphiphile-Based Deep Eutectic Solvents

Deep eutectic solvents (DESs) are an emerging class of modern, often “green” solvents with unique properties. Recently, a deep eutectic system based on amphiphilic surfactant N-alkyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (C12 & C14 sulfobetaine) and (1S)-(+)-10-camphor-sulfonic acid in the molar ratio 1:1.5 has been reported. Nanostructuring can be expected in this DES due to the nature of the components. In this work, we have investigated the native nanostructure in the DES comprising C12–C18 alkyl chain sulfobetaines with camphor sulfonic acid and how it interacts with polar and nonpolar species, water and dodecane, respectively, using small angle neutron scattering. By using contrast variation to highlight the relative position of the solvent components and additives, we can resolve the structure of the solvent and how it changes upon interaction with water and dodecane. Scattering from the neat DES shows structures corresponding to the self-assembly of sulfobetaines; the size of the structure increases as the alkyl chain length of the sulfobetaines increases. Water and dodecane interact, respectively, with the hydrophilic and hydrophobic moieties in the DES structure, primarily the sulfobetaine, thereby swelling and solvating the entire structure. The extent of the shift of the peak position, and the swelling, depend on concentration of the additive. The solution phase organization and the interaction of polar and nonpolar species as observed here, have the potential to affect the ordering of inorganic or polymeric materials grown in such solvents, paving new avenues for templating applications

Creating transient gradients in supramolecular hydrogels

The self‐assembly of low molecular weight gelators in water usually produces homogeneous hydrogels. However, homogeneous gels are not always desired. Using a photoacid generator, it is shown how to form gels with a transient gradient in stiffness, proved using cavitation and bulk rheology. Small‐angle neutron scattering is used to show that the gels formed by photoacid are the result of the same structures as when using a conventional pH trigger. Patterned gels can also be formed, again with transient differences in stiffness

A small-angle neutron scattering environment for in-situ observation of chemical processes

A new sample environment for the observation of ongoing chemical reactions is introduced for small-angle neutron scattering (SANS) experiments which enables structural changes to be followed continuously across a wide Q-range in response to changes in the chemical environment. The approach is demonstrated and validated by performing single and multiple potentiometric titrations on an aqueous anionic surfactant solution (oligo-oxyethylene alkylether carboxylic acid in D2O) with addition times varying from 1s to 2h. It is shown that the continuous flow set-up offers considerable advantages over classical ‘static’ measurements with regards to sample throughput, compositional precision and the ability to observe fast structural transitions. Finally, the capabilities and ongoing optimisation of the sample environment are discussed with reference to potential applications in the fields of biology, colloidal systems and complex soft matter.DFG, 325093850, Open Access Publizieren 2017 - 2018 / Technische Universität Berli

Controlling And Understanding Single And Multicomponent Supramolecular Gels

Supramolecular gels can be prepared by the self-assembly of small molecules into fibrous structures. The properties of the resulting gels depend on how the gels are formed, such that gels with very different properties can be prepared from a single gelator if different gelation methods are used. We have been working to understand this, and for example can prepare gels that can or cannot be 3D-printed from the same gelator by varying gelation method. Here, we will focus on explaining the design rules. As specific examples, we will discuss how varying the chirality of our dipeptide-based gelators can be used to control the self-assembled aggregates, leading to differences in the final gels. We will also show how our understanding can be expanded to multicomponent systems, where each component gelator can form gels alone. In these mixed systems, we can control assembly such that self-sorted multicomponent gels are formed. We will show how such systems can be characterised to prove this assembly and how this approach can be used to prepare gels with controlled and specific properties

Insight into the self-assembly of water-soluble perylene bisimide derivatives through a combined computational and experimental approach

We use a combination of computational and experimental techniques to study the self-assembly and gelation of water-soluble perylene bisimides derivatised at the imide position with an amino acid. Specifically, we study the likely structure of self-assembled aggregates of the alanine-functionalised perylene bisimide (PBI-A) and the thermodynamics of their formation using density functional theory and predict the UV-vis spectra of such aggregates using time-dependent density functional theory. We compare these predictions to experiments in which we study the evolution of the UV-Vis and NMR spectra and rheology of alkaline PBI-A solutions when gradually decreasing the pH. Based on the combined computational and experimental results, we show that PBI-A self-assembles at all pH values but that aggregates grow in size upon protonation. Hydrogel formation is driven not by aggregate growth but reduction of the aggregation surface-charge and a decrease in the colloidal stability of the aggregation with respect to agglomeration

Emulsion ripening through molecular exchange at droplet contacts

Two coarsening mechanisms of emulsions are well established: droplet coalescence (fusion of two droplets) and Ostwald ripening (molecular exchange through the continuous phase). Here a third mechanism is identified, contact ripening, which operates through molecular exchange upon droplets collisions. A contrast manipulated small‐angle neutron scattering experiment was performed to isolate contact ripening from coalescence and Ostwald ripening. A kinetic study was conducted, using dynamic light scattering and monodisperse nanoemulsions, to obtain the exchange key parameters. Decreasing the concentration or adding ionic repulsions between droplets hinders contact ripening by decreasing the collision frequency. Using long surfactant chains and well‐hydrated heads inhibits contact ripening by hindering fluctuations in the film. Contact ripening can be controlled by these parameters, which is essential for both emulsion formulation and delivery of hydrophobic ingredients

Neutralisation rate controls the self-assembly of pH-sensitive surfactants

The degree of ionisation of a weakly acidic surfactant can be continuously modified from nonionic to ionic by adjusting the pH. This property can be used to control the curvature and therefore the morphology of the self-assembled aggregates it forms in solution. Herein, we report the surprising phenomenon, observed in the alkyl ether oligo(ethylene oxide) carboxylate (CH3(CH2)11/13OEO4.5CH2COOH), whereby it is not only the pH but also the neutralisation rate that affects the aggregate morphology. Specifically, when the pH is increased slowly, up to 40 wt% of the surfactant remains in a long-lived vesicle state at high pH. This phenomenon was characterised in detail by small-angle neutron scattering and light scattering techniques. The cause of this phenomenon is thought to be related to a combination of polydispersity and the formation of acid-carboxylate dimers close to the pKa. The transition of these vesicles to the thermodynamically favoured micelles at high pH is inhibited by a high activation energy barrier and therefore only occurs very slowly. Increasing the NaCl concentration eliminates the presence of vesicles at high pH, demonstrating that the activation energy for the vesicle-to-micelle transition depends strongly on electrostatic interactions. These experiments show that the preparation pathway can be used to obtain different self-assembled structures at identical conditions via kinetic control. This phenomenon provides a useful tool for devising formulations where the properties of the system can be altered without changing the composition.BMBF, 05K16KT1, SANS an funktionalen Soft-Matter Proben während des Herstellungsprozesses und in komplexen UmgebungenTU Berlin, Open-Access-Mittel - 201

On the mesoscopic origins of high viscosities in some polyelectrolyte-surfactant mixtures

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in J. Chem. Phys. 143, 074902 (2015) and may be found at https://doi.org/10.1063/1.4928583.Oppositely charged polyelectrolyte (PE) surfactant mixtures allow the control of rheological parameters of a solution even at fairly low concentrations. For example, addition of 0.3 wt. % of anionic surfactant to a 1 wt. % solution of the polycation JR 400 increases the viscosity by 4 orders of magnitude. Recently, we could show that this increase is related to the formation of mixed, rod-like PE/surfactant aggregates which interconnect several polyelectrolyte chains [Hoffmann et al., Europhys. Lett. 104, 28001 (2013)]. In this paper, we refine our structural model of the aggregates to obtain a more consistent picture of their internal structure for different anionic surfactants. Combining small angle neutron scattering (SANS) and neutron spin-echo (NSE) allows us to determine the size of the aggregates. By comparing different contrasts, the internal structure of the aggregates can be elucidated and it is seen that the PE in the aggregates retains a relatively high freedom of movement. We proceeded to investigate the influence of the surfactant concentration and the surfactant type on structure and dynamics of the mixed aggregates. It is seen that the structural parameters of the aggregates depend very little on the surfactant concentration and headgroup. However, it is crucial to incorporate a sufficient amount of PE in the aggregates to increase the viscosity of the aggregates. By comparing viscous samples at 1 wt. % PE concentration with samples at a PE concentration of 0.3 wt. %, where no significant increase in viscosity is observed, we find that similar aggregates are formed already at this lower PE concentrations. However, the amount of PE incorporated in them is insufficient to interconnect several PE chains and therefore, they do not increase viscosity. So, our detailed investigation combining contrast variation SANS and NSE does not only allow to explain the viscosity behavior but also to deduced detailed information regarding the structures and the dynamics especially of the polyelectrolyte within the complexes.BMBF, 05K13KT1, Probenumgebung und paralle Charakterisierung bei hochpräzisen Neutronen Spin-Echo (NSE) Messungen an komplexen Systemen der weichen Materi

Direct small angle neutron scattering observation of stretched chain conformation in nanocomposites: more insight of polymer contributions in mechanical reinforcement

International audienceIn this paper we present a direct measurement of stretched chain conformation in polymer nanocomposites in a large range of deformation using a specific contrast-matched SANS method. Whatever the filler structure and the chain length the results show a clear identity of chain deformation in pure and reinforced polymer and offer a new insight of the polymer chain contribution in the mechanical reinforcement. It suggests that glassy layer or glassy paths, recently proposed, should involve only a small fraction of chains. As a result, the remaining filler contribution appears strikingly constant with deformation as explained by continuous locking-unlocking rearrangement process of the particles