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1.
Nat Commun ; 15(1): 4860, 2024 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-38849412

RESUMO

Magnetic skyrmions are topologically protected magnetization vortices that form three-dimensional strings in chiral magnets. With the manipulation of skyrmions being key to their application in devices, the focus has been on their dynamics within the vortex plane, while the dynamical control of skyrmion strings remained uncharted territory. Here, we report the effective bending of three-dimensional skyrmion strings in the chiral magnet MnSi in orthogonal thermal gradients using small angle neutron scattering. This dynamical behavior is achieved by exploiting the temperature-dependent skyrmion Hall effect, which is unexpected in the framework of skyrmion dynamics. We thus provide experimental evidence for the existence of magnon friction, which was recently proposed to be a key ingredient for capturing skyrmion dynamics, requiring a modification of Thiele's equation. Our work therefore suggests the existence of an extra degree of freedom for the manipulation of three-dimensional skyrmions.

2.
Langmuir ; 2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38917358

RESUMO

The lipids located in the outermost layer of the skin, the stratum corneum (SC), play a crucial role in maintaining the skin barrier function. The primary components of the SC lipid matrix are ceramides (CERs), cholesterol (CHOL), and free fatty acids (FFAs). They form two crystalline lamellar phases: the long periodicity phase (LPP) and the short periodicity phase (SPP). In inflammatory skin conditions like atopic dermatitis and psoriasis, there are changes in the SC CER composition, such as an increased concentration of a sphingosine-based CER (CER NS) and a reduced concentration of a phytosphingosine-based CER (CER NP). In the present study, a lipid model was created exclusively forming the SPP, to examine whether alterations in the CER NS:CER NP molar ratio would affect the lipid organization. Experimental data were combined with molecular dynamics simulations of lipid models containing CER NS:CER NP at ratios of 1:2 (mimicking a healthy SC ratio) and 2:1 (observed in inflammatory skin diseases), mixed with CHOL and lignoceric acid as the FFA. The experimental findings show that the acyl chains of CER NS and CER NP and the FFA are in close proximity within the SPP unit cell, indicating that CER NS and CER NP adopt a linear conformation, similarly as observed for the LPP. Both the experiments and simulations indicate that the lamellar organization is the same for the two CER NS:CER NP ratios while the SPP NS:NP 1:2 model had a slightly denser hydrogen bonding network than the SPP NS:NP 2:1 model. The simulations show that this might be attributed to intermolecular hydrogen bonding with the additional hydroxide group on the headgroup of CER NP compared with CER NS.

3.
Small ; : e2311109, 2024 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-38597752

RESUMO

Controlling the nanomorphology in bulk heterojunction photoactive blends is crucial for optimizing the performance and stability of organic photovoltaic (OPV) technologies. A promising approach is to alter the drying dynamics and consequently, the nanostructure of the blend film using solvent additives such as 1,8-diiodooctane (DIO). Although this approach is demonstrated extensively for OPV systems incorporating fullerene-based acceptors, it is unclear how solvent additive processing influences the morphology and stability of nonfullerene acceptor (NFA) systems. Here, small angle neutron scattering (SANS) is used to probe the nanomorphology of two model OPV systems processed with DIO: a fullerene-based system (PBDB-T:PC71BM) and an NFA-based system (PBDB-T:ITIC). To overcome the low intrinsic neutron scattering length density contrast in polymer:NFA blend films, the synthesis of a deuterated NFA analog (ITIC-d52) is reported. Using SANS, new insights into the nanoscale evolution of fullerene and NFA-based systems are provided by characterizing films immediately after fabrication, after thermal annealing, and after aging for 1 year. It is found that DIO processing influences fullerene and NFA-based systems differently with NFA-based systems characterized by more phase-separated domains. After long-term aging, SANS reveals both systems demonstrate some level of thermodynamic induced domain coarsening.

4.
RSC Adv ; 14(18): 12888-12896, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38650684

RESUMO

Cellulose membranes were prepared from an EMIMAc ionic liquid solution by nonsolvent-induced phase separation (NIPS) in coagulation baths of water-acetone mixtures, ethanol-water mixtures and water at different temperatures. High water volume fractions in the coagulation bath result in a highly reproducible gel-like structure with inhomogeneities observed by small-angle neutron scattering (SANS). A structural transition of cellulose takes place in water-acetone baths at very low water volume fractions, while a higher water bath temperature increases the size of inhomogeneities in the gel-like structure. These findings demonstrate the value of SANS for characterising and understanding the structure of regenerated cellulose films in their wet state. Such insights can improve the engineering and structural tuning of cellulose membranes, either for direct use or as precursors for carbon molecular sieve membranes.

5.
Nano Lett ; 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38591912

RESUMO

Deviations between macrorheological and particle-based microrheological measurements are often considered to be a nuisance and neglected. We study aqueous poly(ethylene oxide) (PEO) hydrogels for varying PEO concentrations and chain lengths that contain microscopic tracer particles and show that these deviations reveal the nanoscopic viscoelastic properties of the particle-hydrogel interface. Based on the transient Stokes equation, we first demonstrate that the deviations are not due to finite particle radius, compressibility, or surface-slip effects. Small-angle neutron scattering rules out hydrogel heterogeneities. Instead, we show that a generalized Stokes-Einstein relation, accounting for an interfacial shell around tracers with viscoelastic properties that deviate from bulk, consistently explains our macrorheological and microrheological measurements. The extracted shell diameter is comparable to the PEO end-to-end distance, indicating the importance of dangling chain ends. Our methodology reveals the nanoscopic interfacial rheology of hydrogels and is applicable to different kinds of viscoelastic fluids and particles.

6.
Biochim Biophys Acta Biomembr ; 1866(5): 184324, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38688405

RESUMO

The stratum corneum (SC) lipid matrix, composed primarily of ceramides (CERs), cholesterol and free fatty acids (FFA), has an important role for the skin barrier function. The presence of the long periodicity phase (LPP), a unique lamellar phase, is characteristic for the SC. Insight into the lipid molecular arrangement within the LPP unit cell is imperative for understanding the relationship between the lipid subclasses and the skin barrier function. In this study, the impact of the CER head group structure on the lipid arrangement and barrier functionality was investigated using lipid models forming the LPP. The results demonstrate that the positions of CER N-(tetracosanoyl)-sphingosine (CER NS) and CER N-(tetracosanoyl)-phytosphingosine (CER NP), two essentials CER subclasses, are not influenced by the addition of another CER subclass (N-(tetracosanoyl)-dihydrosphingosine (CER NdS), N-(2R-hydroxy-tetracosanoyl)-sphingosine (CER AS) or D-(2R-hydroxy-tetracosanoyl)-phytosphingosine (CER AP)). However, differences are observed in the lipid organization and the hydrogen bonding network of the three different models. A similar localization of CER NP and CER NS is also observed in a more complex lipid model, with the CER subclass composition mimicking that of human SC. These studies show the adaptability and insensitivity of the LPP unit cell structure to changes in the lipid head group structures of the CER subclasses.


Assuntos
Ceramidas , Epiderme , Ceramidas/química , Humanos , Epiderme/metabolismo , Epiderme/química , Esfingosina/análogos & derivados , Esfingosina/química , Esfingosina/metabolismo , Colesterol/química , Colesterol/metabolismo
7.
Soft Matter ; 19(44): 8507-8518, 2023 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-37889133

RESUMO

A series of block copolymers comprising styrene and maleic acid (SMA) has been prepared using RAFT polymerisation. RAFT often results in a large hydrophobic alkylthiocarbonylthio end group and this work examines its effect on the solution behaviour of the copolymers. SMA variants with, and without, this end group were synthesised and their behaviour compared with a commercially-available random copolymer of similar molecular weight. Dynamic light scattering and surface tension measurements found the RAFT-copolymers preferentially self-assembled into higher-order aggregates in aqueous solution. Small angle neutron scattering using deuterated styrene varients add support to the accepted model that these agreggates comprise a solvent-protected styrenic core with an acid-rich shell. Replacing the hydrophobic RAFT end group with a more hydrophilic nitrile caused differences in the resulting surface activity, attributed to the ability of the adjoining styrene homoblock to drive aggregation. Each of the copolymers formed SMALP nanodiscs with DMPC lipids, which were found to encapsulate a model membrane protein, gramicidin. However, end group variation affected solubilisition of DPPC, a lipid with a higher phase transition temperature. When using RAFT-copolymers terminated with a hydrophobic group, swelling of the bilayer and greater penetration of the homoblock into the nanodisc core occurred with increasing homoblock length. Conversely, commercial and nitrile-terminated RAFT-copolymers produced nanodisc sizes that stayed constant, instead indicating interaction at the edge of the lipid patch. The results highlight how even minor changes to the copolymer can modify the amphiphilic balance between regions, knowledge useful towards optimising copolymer structure to enhance and control nanodisc formation.

8.
J Lipid Res ; 64(8): 100400, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-37301511

RESUMO

The lipids in the uppermost layer of the skin, the stratum corneum (SC), play an important role in the skin barrier function. The three main subclasses in the SC lipid matrix are ceramides (CER), cholesterol, and free fatty acids. In inflammatory skin diseases, such as atopic dermatitis and psoriasis, the SC lipid composition is modulated compared to the composition in healthy SC. One of the main alterations is the molar ratio between the concentration of CER N-(tetracosanoyl)-sphingosine (CER NS) and CER N-(tetracosanoyl)-phytosphingosine (CER NP), which correlated with an impaired skin barrier function. In the present study, we investigated the impact of varying the CER NS:CER NP ratios on the lipid organization, lipid arrangement, and barrier functionality in SC lipid model systems. The results indicate that a higher CER NS:CER NP ratio as observed in diseased skin did not alter the lipid organization or lipid arrangement in the long periodicity phase encountered in SC. The trans-epidermal water loss, an indication of the barrier functionality, was significantly higher for the CER NS:CER NP 2:1 model (mimicking the ratio in inflammatory skin diseases) compared to the CER NS:CER NP 1:2 ratio (in healthy skin). These findings provide a more detailed insight into the lipid organization in both healthy and diseased skin and suggest that in vivo the molar ratio between CER NS:CER NP contributes to barrier impairment as well but might not be the main factor.


Assuntos
Psoríase , Esfingosina , Humanos , Ceramidas , Pele , Epiderme
9.
Rev Sci Instrum ; 94(3): 033901, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-37012763

RESUMO

Neutron resonance spin echo (NRSE) technique has the potential to increase the Fourier time and energy resolution in neutron scattering by using radio frequency (rf) neutron spin-flippers. However, aberrations arising from variations in the neutron path length between the rf flippers reduce the polarization. Here, we develop and test a transverse static-field magnet, a series of which are placed between the rf flippers, to correct for these aberrations. The prototype correction magnet was both simulated in an NRSE beamline using McStas, a Monte Carlo neutron ray-tracing software package, and measured using neutrons. The results from the prototype demonstrate that this static-field design corrects for transverse-field NRSE aberrations.

10.
Chemistry ; 29(37): e202301042, 2023 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-37067953

RESUMO

pH dependence on water soluble aggregates is well-known in the field of low molecular weight gelators (LMWGs), with different aggregates sometimes having very different properties depending on their final pH. This aggregation determines their applications and performance. Here, we investigate the pH dependence of perylene bisimide gels; initially solutions are formed at a high pH and gels form as the pH is decreased. We find it is not only the final pH but also the starting pH that can impact the resulting gel. We use small angle neutron scattering (SANS), rheology, 1 H NMR spectroscopy and absorption spectroscopy to examine the effect of starting pH on gelation kinetics and final gel properties. Adjusting the solution from pH 9 (where there are few or no aggregates) to pH 6 results in the formation of different worm-like micelles than the ones directly formed at pH 6, leading to again gels with different mechanical properties. This work highlights the importance of controlling the pH of solutions before gelation, but also opens up more possible morphologies and therefore more properties from the same molecule.

11.
J Chem Phys ; 158(3): 034901, 2023 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-36681636

RESUMO

In this work, we studied TEMPO-oxidized cellulose nanofibril (OCNF) suspensions in the presence of diverse surfactants. Using a combination of small angle neutron scattering (SANS) and rheology, we compared the physical properties of the suspensions with their structural behavior. Four surfactants were studied, all with the same hydrophobic tail length but different headgroups: hexaethylene glycol mono-n-dodecyl ether (C12EO6, nonionic), sodium dodecyl sulfate (SDS, anionic), cocamidopropyl betaine (CapB, zwitterionic), and dodecyltrimethylammonium bromide (DTAB, cationic). Contrast variation SANS studies using deuterated version of C12EO6 or SDS, or by varying the D2O/H2O ratio of the suspensions (with CapB), allowed focusing only on the structural properties of OCNFs or surfactant micelles. We showed that, in the concentration range studied, for C12EO6, although the nanofibrils are concentrated thanks to an excluded volume effect observed in SANS, the rheological properties of the suspensions are not affected. Addition of SDS or CapB induces gelation for surfactant concentrations superior to the critical micellar concentration (CMC). SANS results show that attractive interactions between OCNFs arise in the presence of these anionic or zwitterionic surfactants, hinting at depletion attraction as the main mechanism of gelation. Finally, addition of small amounts of DTAB (below the CMC) allows formation of a tough gel by adsorbing onto the OCNF surface.


Assuntos
Celulose Oxidada , Tensoativos , Tensoativos/química , Espalhamento a Baixo Ângulo , Dodecilsulfato de Sódio/química
12.
Langmuir ; 38(39): 11845-11859, 2022 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-36121768

RESUMO

We report the synthesis of a new conjugated polymer bearing crown ether moieties, poly[(N(1-aza-[18]crown-6)carbamido)thiophene-2,5-diyl-alt-1,4-phenylene] (BG2). In water, BG2 forms a dispersion with a slightly cloudy appearance. We have studied the effect of adding surfactants, with different polar head groups, on these polymer-polymer aggregates. Special attention is given to the system with the anionic surfactant, sodium dodecyl sulfate (SDS). The combination of photophysical techniques with electrical conductivity, NMR (1H, 13C, and 27Na), DFT calculations, molecular dynamics simulations, and small-angle neutron scattering (SANS) provides a detailed picture on the behavior of the SDS/BG2 system in aqueous solution and in thin films. NMR, electric conductivity, and DFT results suggest that hydrophilic interactions occur between the polar headgroup of the surfactant (OSO3- Na+) and the aza-[18]-crown-6 moiety. DFT calculations confirmed the capability of BG2 to form stable complexes with the Na+ cations, where the cation can be either inside the azacrown cavity or sandwiched between the cavity and the polymer chain, which seem to determine the position of the surfactant hydrocarbon chain and, therefore, be responsible for the disruption of the BG2 aggregates and subsequent increase in the photoluminescence quantum yields. SANS measurements, made with hydrogenated and deuterated SDS in D2O, clearly show how micron-sized aggregates of BG2 are broken down by SDS and then how BG2 becomes preferentially incorporated within joint colloidal particles of BG2 and SDS with increasing [SDS]/[BG2] molar ratio.

13.
J Lipid Res ; 63(9): 100258, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-35931203

RESUMO

Understanding the lipid arrangement within the skin's outermost layer, the stratum corneum (SC), is important for advancing knowledge on the skin barrier function. The SC lipid matrix consists of ceramides (CERs), cholesterol, and free fatty acids, which form unique crystalline lamellar phases, referred to as the long periodicity phase (LPP) and short periodicity phases. As the SC lipid composition is complex, lipid model systems that mimic the properties of native SC are used to study the SC lipid organization and molecular arrangement. In previous studies, such lipid models were used to determine the molecular organization in the trilayer structure of the LPP unit cell. The aim of this study was to examine the location of CER N-(tetracosanoyl)-phytosphingosine (CER NP) in the unit cell of this lamellar phase and compare its position with CER N-(tetracosanoyl)-sphingosine (CER NS). We selected CER NP as it is the most prevalent CER subclass in the human SC, and its location in the LPP is not known. Our neutron diffraction results demonstrate that the acyl chain of CER NP was positioned in the central part of the trilayer structure, with a fraction also present in the outer layers, the same location as determined for the acyl chain of CER NS. In addition, our Fourier transformed infrared spectroscopy results are in agreement with this molecular arrangement, suggesting a linear arrangement for the CER NS and CER NP. These findings provide more detailed insight into the lipid organization in the SC lipid matrix.


Assuntos
Ceramidas , Esfingosina , Ceramidas/química , Colesterol/química , Epiderme/química , Ácidos Graxos não Esterificados/química , Humanos , Pele/química , Esfingosina/análogos & derivados , Esfingosina/análise
14.
Artigo em Inglês | MEDLINE | ID: mdl-35819416

RESUMO

Activity tests for synthetic antimicrobial compounds are often limited to the minimal inhibitory concentration assay using standard media and bacterial strains. In this study, a family of acrylamide copolymers that act as synthetic mimics of antimicrobial peptides were synthesized and shown to have a disruptive effect on bacterial membranes and structural integrity through microscopy techniques and membrane polarization experiments. The polymers were tested for their antimicrobial properties using media that mimic clinically relevant conditions. Additionally, their activity was compared in two different strains of the Gram-positive bacterium Staphylococcus aureus and the Gram-negative bacterium Pseudomonas aeruginosa. We showed that the medium composition can have an important influence on the polymer activity as there was a considerable reduction in minimal inhibitory concentrations against S. aureus grown in synthetic wound fluid (SWF), and against P. aeruginosa grown in synthetic cystic fibrosis sputum media (SCFM), compared to the concentrations in standard testing media. In contrast, we observed a complete loss of activity against P. aeruginosa in the serum-containing SWF. Finally, we made use of an emerging invertebrate in vivo model, using Galleria mellonella larvae, to assess toxicity of the polymeric antimicrobials, showing a good correlation with cell line toxicity measurements and demonstrating its potential in the evaluation of novel antimicrobial materials.

15.
Biochim Biophys Acta Biomembr ; 1864(6): 183886, 2022 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-35143742

RESUMO

The stratum corneum's lipid matrix is a critical for the skin's barrier function and is primarily composed of ceramides (CERs), cholesterol (CHOL) and free fatty acids (FFAs). The lipids form a long periodicity phase (LPP), a unique trilayer unit cell structure. An enzyme driven pathway is implemented to synthesize these key lipids. If these enzymes are down- or upregulated as in inflammatory diseases, the final lipid composition is affected often altering the barrier function. In this study, we mimicked down regulation of enzymes involved in the synthesis of the sphingosine and CER amide bond. In a LPP lipid model, we substituted CER N-(tetracosanoyl)-sphingosine (CER NS) with either i) FFA C24 and free sphingosine, to simulate the loss of the CER amide bond, or ii) with FFA C24 and C18 to simulate the loss of the sphingosine headgroup. Our study shows the lipids in the LPP would not phase separate until at least 25% of the CER NS is substituted keeping the lateral packing and conformational ordering unaltered. Neutron diffraction studies showed that free sphingosine chains localized at the outer layers of the unit cell, while the remaining CER NS head group was concentrated in the inner headgroup layers. However, when FFA C18 was inserted, CER NS was dispersed throughout the LPP, resulting in an even distribution between the inner and outer water layers. The presented results highlight the importance of the CER NS headgroup structure and its interaction in combination with the carbon chain invariability for optimal lipid arrangement.


Assuntos
Ceramidas , Esfingosina , Ceramidas/química , Ácidos Graxos não Esterificados/análise , Ácidos Graxos não Esterificados/química , Difração de Nêutrons , Pele/química
16.
J Colloid Interface Sci ; 613: 297-310, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35042030

RESUMO

HYPOTHESIS: The milder interaction with biosystems makes the zwitterionic surfactants an important class of surfactants, and they are widely used in biological applications and in personal care formulations. An important aspect of those applications is their strong synergistic interaction with anionic surfactants. It is anticipated that the strong interaction will significantly affect the adsorption and self-assembly properties. EXPERIMENTS: Surface tension, ST, neutron reflectivity, NR, and small angle neutron scattering, SANS, have been used here to explore the synergistic mixing in micelles and at the air-water interface for the zwitterionic surfactant, dodecyldimethylammonium propanesulfonate, C12SB, and the anionic surfactants, alkyl ester sulfonate, AES, in the absence and presence of electrolyte, 0.1 M NaCl. FINDINGS: At the air-water interface the asymmetry of composition in the strong synergistic interaction and the changes with added electrolyte and anionic surfactant structure reflect the relative contributions of the electrostatic and steric interactions to the excess free energy of mixing. In the mixed micelles the synergy is less pronounced and indicates less severe packing constraints. The micelle structure is predominantly globular to elongated, and shows a pronounced micellar growth with composition which depends strongly upon the nature of the anionic surfactant and the addition of electrolyte.


Assuntos
Micelas , Água , Eletricidade Estática , Tensão Superficial , Tensoativos
17.
Langmuir ; 37(42): 12512-12517, 2021 10 26.
Artigo em Inglês | MEDLINE | ID: mdl-34647752

RESUMO

We examine the formation and growth of isolated myelin figures and microscale multilamellar tubules from isotropic micellar solutions of an anionic surfactant. Upon cooling, surfactant micelles transform into multilamellar vesicles (MLVs) whose contact is found to trigger the unidirectional growth of myelins. While the MLV diameter grows as dMLV ∝ t1/2, myelins grow linearly in time as LM ∝ t1, with a fixed diameter. Combining time-resolved small-angle neutron scattering (SANS) and optical microscopy, we demonstrate that the microscopic growth of spherical MLVs and cylindrical myelins stems from the same nanoscale molecular mechanism, namely, the surfactant exchange from micelles into curved lamellar structures at a constant volumetric rate. This mechanism successfully describes the growth rate of (nonequilibrium) myelin figures based on a population balance at thermodynamic equilibrium.


Assuntos
Bainha de Mielina , Tensoativos , Micelas , Espalhamento a Baixo Ângulo , Termodinâmica
18.
Polymers (Basel) ; 13(16)2021 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-34451340

RESUMO

Oppositely charged polymer-surfactant complexes are frequently explored as a function of phase space defined by the charge ratio Z, (where Z = [+polymer]/[-surfactant]), commonly accessed through the surfactant concentration. Tuning the phase behaviour and related properties of these complexes is an important tool for optimising commercial formulations; hence, understanding the relationship between Z and bulk properties is pertinent. Here, within a homologous series of cationic hydroxyethyl cellulose (cat-HEC) polymers with minor perturbations in the degree of side chain charge modification, phase space is instead explored through [+polymer] at fixed Cpolymer. The nanostructures were characterised by small-angle neutron scattering (SANS) in D2O solutions and in combination with the oppositely charged surfactant sodium dodecylsulfate (h- or d-SDS). Scattering consistent with thin rods with an average radius of ∼7.7 Šand length of ∼85 Šwas observed for all cat-HEC polymers and no significant interactions were shown between the neutral HEC polymer and SDS (CSDS < CMC). For the charge-modified polymers, interactions with SDS were evident and the radius of the formed complexes grew up to ∼15 Šwith increasing Z. This study demonstrates a novel approach in which the Z phase space of oppositely charged polymer-surfactant complexes can be controlled at fixed concentrations.

19.
J Colloid Interface Sci ; 582(Pt B): 1116-1127, 2021 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-32942067

RESUMO

Aqueous mixtures of anionic and nonionic/cationic surfactants can form non-trivial self-assemblies in solution and exhibit macroscopic responses. Here, we investigate the micellar phase of pure and mixed aqueous solutions of Sodium Dodecyl Sulfate (SDS) and Dimethyldodecyl Amine Oxide (DDAO) using a combination of Small Angle Neutron Scattering (SANS), Fourier-Transform Infrared Spectroscopy (FTIR) and rheological measurements. We examine the effect of temperature (0-60 °C), on the 20 wt% SDS micellar solutions with varying DDAO (⩽5 wt%), and seek to correlate micellar structure with zero-shear solution viscosity. SANS establishes the formation of prolate ellipsoidal micelles in aqueous solutions of pure SDS, DDAO and SDS/DDAO mixtures, whose axial ratio is found to increase upon cooling. Elongation of the ellipsoidal micelles of pure SDS is also induced by the introduction of the non-anionic DDAO, which effectively reduces the repulsive interactions between the anionic SDS head-groups. In FTIR measurements, the formation of elongated mixed ellipsoidal micelles is confirmed by the increase of ordering in the hydrocarbon chain tails and interaction between surfactant head-groups. We find that the zero-shear viscosity of the mixed surfactant solutions increases exponentially with decreasing temperature and increasing DDAO content. Significantly, a master curve for solution viscosity can be obtained in terms of micellar aspect ratio, subsuming the effects of both temperature and DDAO composition in the experimental range investigated. The intrinsic viscosity of mixed micellar solutions is significantly larger than the analytical and numerical predictions for Brownian suspensions of ellipsoidal colloids, highlighting the need to consider interactions of soft micelles under shear, especially at high concentrations.

20.
J Colloid Interface Sci ; 586: 190-199, 2021 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-33162043

RESUMO

HYPOTHESIS: Surfactants have been widely used as adjuvants in agri-sprays to enhance the solubility of pesticides in foliar spray deposits and their mobility through leaf cuticles. Previously, we have characterised pesticide solubilisation in nonionic surfactant micelles, but what happens when pesticides become solubilised in anionic, cationic and zwitterionic and their mixtures with nonionic surfactants remain poorly characterised. EXPERIMENTS: To facilitate characterisations by SANS and NMR, we used nonionic surfactant hexaethylene glycol monododecyl ether (C12E6), anionic sodium dodecylsulphate (SDS), cationic dodecyltrimethylammonium bromide (DTAB) and zwitterionic dodecylphosphocholine (C12PC) as model adjuvant systems to solubilise 3 pesticides, Cyprodinil (CP), Azoxystrobin (AZ) and Difenoconazole (DF), representing different structural features. The investigation focused on the influence of solubilisates in driving changes to the micellar nanostructures in the absence or presence of electrolytes. NMR and NOESY were applied to investigate the solubility and location of each pesticide in the micelles. SANS was used to reveal subtle changes to the micellar structures due to pesticide solubilisation with and without electrolytes. FINDINGS: Unlike nonionic surfactants, the ionic and zwitterionic surfactant micellar structures remain unchanged upon pesticide solubilisation. Electrolytes slightly elongate the ionic surfactant micelles but have no effect on nonionic and zwitterionic surfactants. Pesticide solubilisation could alter the structures of the binary mixtures of ionic/zwitterionic and ionic/nonionic micelles by causing elongation, shell shrinkage and dehydration, with the exact alteration being determined by the molar ratio in the mixture.

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