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Even in the absence of surfactants, polymers, or particles, spontaneous emulsions produced by dilution with water can be stable over days. This "Ouzo effect" used by the industry is obtained by rapid dilution from an identified "pre-Ouzo" domain of composition where weak aggregates are present: nanometer-sized clusters covered by a surface layer enriched in a hydrotrope such as ethanol. In these systems, Ostwald ripening is not an effective destabilizing mechanism. Using in situ autodilution small-angle X-ray scattering (SAXS), we follow the morphological transitions occurring in a ternary mixture of water/n-octanol/ethanol throughout the monophasic and biphasic regions. This allows for the first time an online characterization of the multiscale coexisting microstructures. Small-angle neutron scattering (SANS) profiles on metastable emulsions as well as phase-separated samples complete the SAXS data, taking advantage of contrast variation via isotopic substitution. After crossing the phase boundary into the two-phase region, coexisting phases are both ternary solutions structured at the nanometer scale when the emulsion is stable. The transition from single phase to two phases is asymmetric around the plait point. When the initial concentration of the hydrotrope is below the minimum hydrotrope concentration (MHC), emulsification failure occurs, i.e., emulsions cream within seconds. Beyond MHC, the low interfacial tension between coexisting ternary fluids results in a Laplace pressure below 100 Pa, explaining the puzzling resilience of spontaneous emulsion to the universal mechanism of Ostwald ripening.
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Driven by the potential applications of ionic liquids (ILs) in many emerging electrochemical technologies, recent research efforts have been directed at understanding the complex ion ordering in these systems, to uncover novel energy storage mechanisms at IL-electrode interfaces. Here, we discover that surface-active ILs (SAILs), which contain amphiphilic structures inducing self-assembly, exhibit enhanced charge storage performance at electrified surfaces. Unlike conventional non-amphiphilic ILs, for which ion distribution is dominated by Coulombic interactions, SAILs exhibit significant and competing van der Waals interactions owing to the non-polar surfactant tails, leading to unusual interfacial ion distributions. We reveal that, at an intermediate degree of electrode polarization, SAILs display optimum performance, because the low-charge-density alkyl tails are effectively excluded from the electrode surfaces, whereas the formation of non-polar domains along the surface suppresses undesired overscreening effects. This work represents a crucial step towards understanding the unique interfacial behaviour and electrochemical properties of amphiphilic liquid systems showing long-range ordering, and offers insights into the design principles for high-energy-density electrolytes based on spontaneous self-assembly behaviour.
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Hard-sphere particles in nonpolar solvents are an essential tool for colloid scientists. Sterically stabilized poly(methyl methacrylate) (PMMA) particles have long been used as the exemplary hard-sphere system. However, neither the particles themselves nor the poly(12-hydroxystearic acid) (PHSA) stabilizer necessary to prevent aggregation in nonpolar solvents are commercially available. To counter this, several alternatives have been proposed. In recent years, there has been an increased interest in poly(dimethylsiloxane) (PDMS) stabilizers as a commercially available alternative to PHSA, yet the structure of particles made in this way is not as well understood as those produced using PHSA. In this work, we employ small-angle neutron scattering to determine the internal structure of PDMS-stabilized PMMA particles, synthesized with and without an additional crosslinking agent. We report data consistent with a homogeneous PMMA core with a linearly decaying PDMS shell. The thickness of the shell was in excess of 50 nm, thicker than the PHSA layer typically used to stabilize PMMA but consistent with reports of the layer thickness for similar molecular weight PDMS at planar surfaces. We also show that the amount of the hydrogenous material in the particle core of the crosslinked particles notably exceeds the amount of added ethylene glycol dimethacrylate crosslinker, suggesting some entrapment of the PDMS stabilizer in the PMMA matrix.
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Origin of life scenarios generally assume an onset of cell formation in terrestrial hot springs or in the deep oceans close to hot vents, where energy was available for non-enzymatic reactions. Membranes of the protocells had therefore to withstand extreme conditions different from what is found on the Earth surface today. We present here an exhaustive study of temperature stability up to 80 °C of vesicles formed by a mixture of short-chain fatty acids and alcohols, which are plausible candidates for membranes permitting the compartmentalization of protocells. We confirm that the presence of alcohol has a strong structuring and stabilizing impact on the lamellar structures. Moreover and most importantly, at a high temperature (> 60 °C), we observe a conformational transition in the vesicles, which results from vesicular fusion. Because all the most likely environments for the origin of life involve high temperatures, our results imply the need to take into account such a transition and its effect when studying the behavior of a protomembrane model.
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The foundations of silk spinning, the structure, storage, and activation of silk proteins, remain highly debated. By combining solution small-angle neutron and X-ray scattering (SANS and SAXS) alongside circular dichroism (CD), we reveal a shape anisotropy of the four principal native spider silk feedstocks from Nephila edulis. We show that these proteins behave in solution like elongated semiflexible polymers with locally rigid sections. We demonstrated that minor ampullate and cylindriform proteins adopt a monomeric conformation, while major ampullate and flagelliform proteins have a preference for dimerization. From an evolutionary perspective, we propose that such dimerization arose to help the processing of disordered silk proteins. Collectively, our results provide insights into the molecular-scale processing of silk, uncovering a degree of evolutionary convergence in protein structures and chemistry that supports the macroscale micellar/pseudo liquid crystalline spinning mechanisms proposed by the community.
Assuntos
Seda , Aranhas , Animais , Dicroísmo Circular , Conformação Molecular , Espalhamento a Baixo Ângulo , Difração de Raios XRESUMO
Late embryogenesis abundant (LEA) proteins comprise a diverse family whose members play a key role in abiotic stress tolerance. As intrinsically disordered proteins, LEA proteins are highly hydrophilic and inherently stress tolerant. They have been shown to stabilise multiple client proteins under a variety of stresses, but current hypotheses do not fully explain how such broad range stabilisation is achieved. Here, using neutron reflection and surface tension experiments, we examine in detail the mechanism by which model LEA proteins, AavLEA1 and ERD10, protect the enzyme citrate synthase (CS) from aggregation during freeze-thaw. We find that a major contributing factor to CS aggregation is the formation of air bubbles during the freeze-thaw process. This greatly increases the air-water interfacial area, which is known to be detrimental to folded protein stability. Both model LEA proteins preferentially adsorb to this interface and compete with CS, thereby reducing surface-induced aggregation. This novel surface activity provides a general mechanism by which diverse members of the LEA protein family might function to provide aggregation protection that is not specific to the client protein.
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Crioprotetores/química , Proteínas Intrinsicamente Desordenadas/química , Adsorção , Ar , Animais , Proteínas de Arabidopsis/química , Fenômenos Biofísicos , Citrato (si)-Sintase/química , Congelamento , Proteínas de Helminto/química , Difração de Nêutrons , Agregados Proteicos , Dobramento de Proteína , Estabilidade Proteica , Proteínas Recombinantes/química , Rabditídios/química , Espalhamento a Baixo Ângulo , Estresse Fisiológico , Suínos , ÁguaRESUMO
C109 is a potent but poorly soluble FtsZ inhibitor displaying promising activity against Burkholderia cenocepacia, a high-risk pathogen for cystic fibrosis (CF) sufferers. To harness C109 for inhalation, we developed nanocrystal-embedded dry powders for inhalation suspension consisting in C109 nanocrystals stabilized with D-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) embedded in hydroxypropyl-ß-cyclodextrin (CD). The powders could be safely re-dispersed in water for in vitro aerosolization. Owing to the presence of a PEG shell, the rod shape and the peculiar aspect ratio, C109 nanocrystals were able to diffuse through artificial CF mucus. The promising technological features were completed by encouraging in vitro/in vivo effects. The formulations displayed no toxicity towards human bronchial epithelial cells and were active against planktonic and sessile B. cenocepacia strains. The efficacy of C109 nanosuspensions in combination with piperacillin was confirmed in a Galleria mellonella infection model, strengthening their potential for combined therapy of B. cenocepacia lung infections.
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Antibacterianos , Proteínas de Bactérias/antagonistas & inibidores , Brônquios/microbiologia , Infecções por Burkholderia/tratamento farmacológico , Burkholderia cenocepacia/crescimento & desenvolvimento , Fibrose Cística/tratamento farmacológico , Proteínas do Citoesqueleto/antagonistas & inibidores , Sistemas de Liberação de Medicamentos , Células Epiteliais/microbiologia , Nanopartículas , Antibacterianos/química , Antibacterianos/farmacologia , Proteínas de Bactérias/metabolismo , Brônquios/metabolismo , Brônquios/patologia , Infecções por Burkholderia/metabolismo , Infecções por Burkholderia/patologia , Linhagem Celular Tumoral , Fibrose Cística/metabolismo , Fibrose Cística/microbiologia , Fibrose Cística/patologia , Proteínas do Citoesqueleto/metabolismo , Células Epiteliais/metabolismo , Células Epiteliais/patologia , Humanos , Nanopartículas/química , Nanopartículas/uso terapêuticoRESUMO
Recently, nanometric ions were shown to adsorb to hydrated neutral surfaces and to bind to the cavities of macrocyclic molecules with an unexpectedly strong affinity arising from a solvent-mediated effect named superchaotropicity. We show here that nano-ions at low concentrations (µm range), similarly to anionic surfactants, induce the spontaneous transformation of a swollen lyotropic lamellar phase of non-ionic surfactant into a vesicle phase. This transition occurs when the neutral lamellae acquire charges, either by adsorption of the nano-ions onto, or by anchoring of the ionic surfactant into the lamellae. In contrast to ionic surfactants, nano-ions strongly dehydrate the neutral surfactant assemblies. As a conclusion, these purely inorganic nanometric ions act as alternatives to the widely used organic ionic surfactants.
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We show here for the first time that short chain poly( N-isopropylacrylamide) (PNIPAM), one of the most famous thermoresponsive polymers, self-assembles in water to form (i) discrete nanometer-globules and (ii) micrometric sheets with nm-thickness upon addition of the well-known Keggin-type polyoxometalate (POM) H3PW12O40 (PW). The type of self-assembly is controlled by PW concentration: at low PW concentrations, PW adsorbs on PNIPAM chains to form globules consisting of homogeneously distributed PWs in PNIPAM droplets of several nm in size. Upon further addition of PW, a phase transition from globules to micrometric sheets is observed for PNIPAMs above a polymer critical chain length, between 18 and 44 repeating units. The thickness of the sheets is controlled by the PNIPAM chain length, here from 44 to 88 repeating units. The PNIPAM sheets are electrostatically stabilized PWs accumulated on each side of the sheets. The shortest PNIPAM chain with 18 repeating units produces PNIPAM/PW globules with 5-20 nm size but no sheets. The PW/PNIPAM self-assembly arises from a solvent mediated mechanism associated with the partial dehydration of PW and of the PNIPAM, which is related to the general propensity of POMs to adsorb on neutral hydrated surfaces. This effect, known as superchaotropy, is further highlighted by the significant increase in the lower critical solubilization temperature (LCST) of PNIPAM observed upon the addition of PW in the mM range. The influence of the POM nature on the self-assembly of PNIPAM was also investigated by using H4SiW12O40 (SiW) and H3PMo12O40 (PMo), i.e. changing the POM's charge density or polarizability in order to get deeper understanding on the role of electrostatics and polarizability in the PNIPAM self-assembly process. We show here that the superchaotropic behavior of POMs with PNIPAM polymers enables the formation and the shape control of supramolecular organic-inorganic hybrids.
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Elastin-like peptides are biopolymers that display LCST behaviour in solution quite similar to other synthetic polymers like polyethylene oxide. Here we study the structure of the peptide GVG(VPGVG)3 in a temperature range of 25 °C to 70 °C with small angle neutron scattering. The LCST for this peptide is outside the experimental range of temperatures. Molecular conformation is well described within the model of a random coil but increasing temperature leads to significant changes. The peptide displays a combination of conformational change and aggregation that show up in the scattering at low and intermediate scattering vector q. The aggregate size is determined from an integral measure of the scattered intensity. It increases with temperature and concentration. For low concentration we find a size variation with temperature that may be related to the collapse of conformation at the inverse temperature transition (ITT).
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Elastina/química , Peptídeos Cíclicos/química , Ligação de Hidrogênio , Peso Molecular , Agregados Proteicos , Conformação Proteica , Temperatura , Temperatura de TransiçãoRESUMO
Hybrid self-assembling nanoparticles (hsaNPs) encapsulating bisphosphonates (BPs) recently showed very promising results in preclinic experiments for the treatment of brain tumor. However, the poor knowledge on the architecture of hybrid nanovectors is certainly one of the main reasons hampering further clinical and industrial development of these technologies. Here we propose to combine different techniques, that is, small angle neutron scattering (SANS) and X-ray Sscattering (SAXS), with cryo-electron transmission microscopy (cryo-TEM) to study the architecture of the final hsaNPs as well as of the four components before the assembling process. Data analysis based on SANS and SAXS experiments suggested a multiple compartment architecture of the final product, consisting of two bilayers sourrounding a core. Structures consisting of two shells surrounding an internal core were also observed in the cryo-TEM analysis. Such high resolution insight, also combined with size distribution and zeta potential of the NPs, provides exhaustive characterization of hsaNPs encapsulating BPs, and it is aimed at supporting further their clinical and industrial development.
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Antineoplásicos/administração & dosagem , Composição de Medicamentos/métodos , Nanopartículas/química , Neoplasias/tratamento farmacológico , Ácido Zoledrônico/administração & dosagem , Microscopia Crioeletrônica , Ácidos Graxos Monoinsaturados/química , Humanos , Lipossomos , Microscopia Eletrônica de Transmissão , Estrutura Molecular , Nanopartículas/ultraestrutura , Difração de Nêutrons/instrumentação , Difração de Nêutrons/métodos , Fosfatidiletanolaminas/química , Polietilenoglicóis/química , Compostos de Amônio Quaternário/química , Espalhamento a Baixo Ângulo , Transferrina/química , Difração de Raios X/instrumentação , Difração de Raios X/métodosRESUMO
Small-angle neutron scattering experiments, supported by molecular dynamics simulations, have been performed on a range of compositions of the [C2mim]1-x[C12mim]x[Tf2N] ionic liquid mixture system. Isotopic contrast variation, through selective deuteration of both cations, has been used to assist in fitting the data to different scattering models. These data, and subsequent fitting, show that the structure of the ionic liquid mixtures changes substantially as a function of composition. Mixtures where x < 0.32 are dominated by aggregates of amphiphilic [C12mim]+ ions in the relatively polar [C2mim][Tf2N] solvent. Compositions where x > 0.32 can be described as bicontinuous, containing networks of both polar and non-polar domains, where the C12 chains of the [C12mim]+ ions percolate through the system to form a continuous non-polar sub-phase. Temperature-dependent scattering experiments suggest that there is relatively little change in bulk structure in these liquids between 20 and 60 °C. The presence of water, however, does influence some aspects of the liquid structure in a composition that is rich in [C2mim][Tf2N] (where x = 0.24).
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A diverse range of molecular surfactants and polymers have been incorporated into aqueous graphene oxide (GO) and reduced graphene oxide (rGO) dispersions in order to understand the complex relationship between surface chemistry, surface forces and interfacial thermodynamics of these materials with typical amphiphiles. Surfactant additives were systematically varied in terms of their charge and hydrophobicity to reveal important structure-function relationships affecting adsorption and interaction with GO and rGO surfaces. Small-angle (and ultra small-angle) neutron scattering was employed to examine and monitor the interactions and self-assembly in each system. Charge was found to be the overriding factor driving adsorption, as cationic surfactants very readily adsorbed to both GO and rGO, whereas anionic surfactants gave little to no evidence of adsorption despite possessing hydrophobic tail-groups. Molecules of neutral charge such as nonionic and zwitterionic surfactants as well as neutral polymers also showed strong affinities for GO and rGO, indicating that dispersion and dipole (induction polarisation) interactions also play a significant role in adsorption with these materials. Modelling the neutron data revealed in many cases a q-2 slope in the low q and ultra low q regions, indicating that scattering was occurring from large, flat surfaces (lamellae or bilayers), suggesting an effective flattening of the sheets in dispersion. The results presented thus help to form a roadmap for the behaviour of GO and rGO with surfactants and polymers, relevant to adsorption, stabilisation, formulation and coating in aqueous environments as adsorbent and functional materials.
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Contrast-variation small-angle neutron scattering (CV-SANS), small-angle X-ray scattering (SAXS), nuclear magnetic resonance (NMR) measurements of diffusion and isothermal titration calorimetry (ITC) are used to gain insight into the aggregation of an alkyl-C60 derivative, molecule 1, in n-hexane, n-decane and toluene as a function of concentration and temperature. Results point to an associative mechanism of aggregation similar to other commonly associating molecules, including non-ionic surfactants or asphaltenes in non-aqueous solvents. Little aggregation is detected in toluene, but small micelle-like structures form in n-alkane solvents, which have a C60-rich core and alkyl-rich shell. The greatest aggregation extent is found in n-hexane, and at 0.1 M the micelles of 1 comprise around 6 molecules at 25 °C. These micelles become smaller when the concentration is lowered, or if the solvent is changed to n-decane. The solution structure is also affected by temperature, with a slightly larger aggregation extent at 10 °C than at 25 °C. At higher concentrations, for example in solutions of 1 above 0.3 M in n-decane, a bicontinuous network becomes apparent. Overall, these findings aid our understanding of the factors driving the assembly of alkyl-π-conjugated hydrophobic amphiphiles such as 1 in solution and thereby represent a step towards the ultimate goal of exploiting this phenomenon to form materials with well-defined order.
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The aggregation and structure of d-α-tocopheryl polyethylene glycol succinate micelles, TPGS-1000, an amphiphilic derivative of vitamin E, were characterized using scattering and spectroscopic methods, and the impact of different cyclodextrins (CDs) on the self-assembly was investigated, with the view of combining these two versatile pharmaceutical excipients in drug formulations. Combined small-angle neutron scattering (SANS), dynamic light scattering, and time-resolved and steady-state fluorescence emission experiments revealed a core-shell architecture with a high aggregation number (Nagg ≈ 100) and a highly hydrated poly(ethylene oxide) corona (â¼11 molecules of solvent per ethylene oxide unit). Micelles form gradually, with no sharp onset. Structural parameters and hydration of the aggregates were surprisingly stable with both temperature and concentration, which is a critical advantage for their use in pharmaceutical formulations. CDs were shown to affect the self-assembly of TPGS in different ways. Whereas native CDs induced the precipitation of a solid complex (pseudopolyrotaxane), methylated ß-CDs led to different outcomes: constructive (micellar expansion), destructive (micellar rupture), or no effect, depending on the number of substituents and whether the substitution pattern was regular or random on the rims of the macrocycle. Time-resolved SANS studies on mixtures of TPGS with regularly dimethylated ß-CD (DIMEB), which ruptures the micelles, revealed an almost instantaneous demicellization (<100 ms) and showed that the process involved the formation of large aggregates whose size evolved over time. Micellar rupture is caused by the formation of a TPGS-DIMEB inclusion complex, involving the incorporation of up to three macrocycles on the tocopherol, as shown by proton nuclear magnetic resonance (NMR) and ROESY NMR. Analysis of NMR data using Hill's equation revealed that the binding is rather cooperative, with the threading of the CD favoring the subsequent inclusion of additional CDs on the aliphatic moiety.
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Ciclodextrinas/química , Micelas , Polietilenoglicóis , Vitamina ERESUMO
BACKGROUND: The acoustic levitation technique is a useful sample handling method for small solid and liquids samples, suspended in air by means of an ultrasonic field. This method was previously used at synchrotron sources for studying pharmaceutical liquids and protein solutions using x-ray diffraction and small angle x-ray scattering (SAXS). METHODS: In this work we combined for the first time this containerless method with small angle neutron scattering (SANS) and synchrotron radiation circular dichroism (SRCD) to study the structural behavior of proteins in solutions during the water evaporation. SANS results are also compared with SAXS experiments. RESULTS: The aggregation behavior of 45µl droplets of lysozyme protein diluted in water was followed during the continuous increase of the sample concentration by evaporating the solvent. The evaporation kinetics was followed at different drying stage by SANS and SAXS with a good data quality. In a prospective work using SRCD, we also studied the evolution of the secondary structure of the myoglobin protein in water solution in the same evaporation conditions. CONCLUSIONS: Acoustic levitation was applied for the first time with SANS and the high performances of the used neutron instruments made it possible to monitor fast container-less reactions in situ. A preliminary work using SRCD shows the potentiality of its combination with acoustic levitation for studying the evolution of the protein structure with time. GENERAL SIGNIFICANCE: This multi-techniques approach could give novel insights into crystallization and self-assembly phenomena of biological compound with promising potential applications in pharmaceutical, food and cosmetics industry. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo.
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Acústica , Dicroísmo Circular , Proteínas/análise , Espalhamento a Baixo Ângulo , Síncrotrons , Animais , Galinhas , Cavalos , Muramidase/análise , Mioglobina/análise , Difração de Nêutrons , Soluções , Análise Espectral , Água/químicaRESUMO
We study the conformation of a polymer (polyethylene glycol) in a nanoscopic soft confinement with attractive walls. The polymer is added to a water-in-oil microemulsion based on the deuterated anionic surfactant AOT, d-octane and D2O. Three different droplet sizes and up to three polymers per droplet are investigated with small angle scattering combining X-rays and neutrons. This allows determining the confinement size and polymer conformation on identical samples. Whereas polymer conformation in bulk is found to be well described with the model of a Gaussian coil its radius of gyration is drastically increased in the droplet. At the same time it is compressed on a local scale. This supports the picture of a polymer strongly adsorbed on the surfactant layer with a thickness of several Angstroms.
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The controlled complex coacervation of oppositely charged hyaluronic acid (Mw ≈ 800-1000 kg mol-1) and chitosan (Mw ≈ 160 kg mol-1, degree of acetylation = 15%) led to hydrogels with controllable properties in terms of elasticity and strength. In this work, we performed desalting by dialysis of high ionic strength solutions of mixed polyelectrolytes and showed that the control of the pH during the polyelectrolyte assembly greatly impacts the mechanical properties of the hydrogel. First, for pHs from 5.5 to 7.5, a slight coacervation was observed due to low chitosan protonation and poor polyelectrolyte associations. Then, for pHs from 3.0 to 5.5, coacervation and syneresis led to free-standing and easy to handle hydrogels. Finally, for pHs from 2.0 to 3.0 (close to the pKa of the hyaluronic acid), we observed the unusual stretchability of these hydrogels that could arise from the pre-folding of hyaluronic acid chains while physical crosslinking was achieved by hyaluronic acid/chitosan polyelectrolyte complexation.
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In the present contribution, the pre-structuring of binary mixtures of hydrotropes and H2O is linked to the solubilisation of poorly water miscible compounds. We have chosen a series of short-chain alcohols as hydrotropes and benzyl alcohol, limonene and a hydrophobic azo-dye (Disperse Red 13) as organic compounds to be dissolved. A very weak pre-structuring is found for ethanol/H2O and 2-propanol/H2O mixtures. Pre-structuring is most developed for binary 1-propanol/H2O and tert-butanol/H2O mixtures and supports the bicontinuity model of alcohol-rich and water-rich domains as already postulated by Anisimov et al. Such a pre-structuring leads to a high solubilisation power for poorly water miscible components (limonene and Disperse Red, characterized by high octanol/water partition coefficients, log(P) values of 4.5 and 4.85), whereas a very weak pre-structuring leads to a high solubilisation power for slightly water miscible components (benzyl alcohol). This difference in solubilisation power can be linked to (i) the formation of mesoscale structures in the cases of ethanol and 2-propanol and (ii) the extension of pre-structures in the cases of 1-propanol and tert-butanol. Three different solubilisation mechanisms could be identified: bulk solubilisation, interface solubilisation and a combination of both. These supramolecular structures in binary and ternary systems were investigated by small-and-wide-angle X-ray and neutron scattering, dynamic light scattering and conductivity measurements (in the presence of small amounts of salt).
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In this contribution, we (i) link the mesoscopic structuring of the binary structured solvent mixture H2O/tert-butanol (TBA) to the kinetics and the efficacy of the oxidation of benzyl alcohol (BA) to the corresponding aldehyde catalyzed by H5PMo10V2O40. We also compare the catalytic efficacy of this reaction in the mesoscopically structured solvent H2O/TBA to an unstructured (or very weakly structured) solvent H2O/ethanol (EtOH). In this context, we (ii) also give a methodological outline on how to study systematically the catalytic efficacy of chemical reactions as a function of the mesoscale structuring of a binary solvent. We demonstrate that the obtained yields of benzyl aldehyde depend on the type of mesoscopic structuring of the binary solvent H2O/TBA. An elevated catalytic performance of at least 100% is found for unstructured binary mixtures H2O/TBA compared to compartmented binary mixtures H2O/TBA. We conclude that compartmentation of both the organic substrate and the catalyst in TBA and water-rich micro phases seems to be unfavorable for the catalytic efficacy.