Showing papers on "Lyotropic liquid crystal published in 2015"
TL;DR: This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic Liquid-based materials, enabling applications in broad areas.
Abstract: Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.
273 citations
TL;DR: This review presents recent progress in glycerol monooleate liquid crystalline phases used as drug delivery vehicles.
147 citations
TL;DR: In this article, the influence of a saturated fatty acid, capric acid (decanoic acid), on the formation of different lyotropic liquid crystalline phases in monoolein-based systems was investigated by synchrotron small angle X-ray scattering (SAXS), cryogenic transmission electron microscopy (cryo-TEM), dynamic light scattering and zeta potential measurements.
Abstract: Monoolein forms self-assembled nanoparticles with various internally ordered nanostructures, including the lyotropic liquid crystalline inverse hexagonal and inverse bicontinuous cubic phases. This study investigated the influence of a saturated fatty acid, capric acid (decanoic acid), on the formation of different lyotropic liquid crystalline phases in monoolein-based systems. The nanoparticles were characterized by synchrotron small angle X-ray scattering (SAXS), cryogenic transmission electron microscopy (cryo-TEM), dynamic light scattering, and zeta potential measurements. The addition of capric acid to monoolein triggered concentration dependent phase changes with the sequence evolving from an inverse primitive cubic phase to inverse double-diamond cubic, inverse hexagonal (HII), and emulsified microemulsions. SAXS and cryo-TEM revealed the formation of both single phase and mixed phases within a nanoparticle. To understand the cytotoxicity effects of the different nanoparticles, cellular cytotoxicity and hemolysis assays were performed. Nanoparticles in emulsion and hexagonal phases were found to be less toxic than cubic phase nanoparticles. The hemolysis assays followed the same trend with cubic phase dispersions causing the highest level of hemoglobin release. In summary, this study showed that the internal lyotropic liquid crystal mesophase structure of self-assembled nanoparticles needs careful consideration in the design of drug delivery vehicles.
86 citations
TL;DR: In this article, the authors provide an overview of recent advances in the state of the art, including methods of preparation and applications in drug delivery, and future research perspectives are identified.
Abstract: Lamellar, cubic and hexagonal mesophases are some of the most common lyotropic liquid crystal systems, and have attracted much research attention because of their distinctive structures and physicochemical properties. Polar lipids and surfactants exhibit a range of phase behavior in an aqueous environment, depending on the composition of the lipids and surfactants. These characteristics have been investigated for a variety of applications in drug delivery, and lyotropic liquid crystal systems have potential as drug carriers for small molecules, peptides, and proteins. In this article we provide an overview of recent advances in the state of the art, including methods of preparation and applications in drug delivery. The scope and limitations of lyotropic liquid crystals for drug delivery are discussed, and future research perspectives are identified.
73 citations
TL;DR: This work presents a comprehensive study of the dimensional structural control of hydrophilic drug release, including 3-d bicontinuous cubic, 2-d lamellar, 1-d hexagonal and 0-d micellar cubic phases in excess water.
71 citations
TL;DR: The rheological results manifest that the formed H1 phase in the C12mimSal/H2O system exhibits an impressive viscoelastic behavior, indicated by a modulus (G' and G″) that is 1 order of magnitude higher than that of C 12mimBr.
Abstract: Two imidazolium-based surface-active ionic liquids with aromatic counterions, namely, 1-dodecyl-3-methylimidazolium salicylate (C12mimSal) and 1-dodecyl-3-methylimidazolium 3-hydroxy-2-naphthoate (C12mimHNC), were synthesized, and their aggregate behavior in aqueous solutions was systematically explored. Surface tension and conductivity measurements indicate that both C12mimSal and C12mimHNC show superior surface activity compared to the common imidazolium-based SAIL with the same hydrocarbon chain length, 1-dodecyl-3-methylimidazolium bromide (C12mimBr). This result demonstrates that the incorporation of aromatic counterions favors the formation of micelles. C12mimHNC displays a higher surface activity than C12mimSal, resulting from the different hydrophobicities of the counterions. In comparison with C12mimBr, C12mimSal not only can form hexagonal liquid-crystalline phase (H1) in aqueous solution, but also exhibits a broad region of cubic liquid-crystalline phase (V2) at higher concentration. As for the C12mimHNC/H2O system, a lamellar liquid-crystalline (L(α)) phase was observed. These lyotropic liquid crystals (LLCs) were characterized by polarized optical microscopy (POM) and small-angle X-ray scattering (SAXS). Structural parameters calculated from SAXS patterns suggest that a higher concentration of the SAIL leads to a denser arrangement whereas a higher temperature results in the opposite effect. The rheological results manifest that the formed H1 phase in the C12mimSal/H2O system exhibits an impressive viscoelastic behavior, indicated by a modulus (G' and G″) that is 1 order of magnitude higher than that of C12mimBr. Density functional theory (DFT) calculations reveal that C12mimSal has a more negative interaction energy with a water molecule and the Sal(-) counterion presents a stronger electronegativity than the HNC(-) counterion. The specific phase behavior of the C12mimSal/H2O and C12mimHNC/H2O systems can be attributed to the strong synergic interaction between the imidazolium cation and the aromatic counterion, including electrostatic attraction, hydrophobic interaction, and especially π-π interaction.
66 citations
TL;DR: In this article, the authors collate and collectively interpret studies in the field of steric stabilization of this important emerging class of nanoparticles for drug and medical imaging agent delivery, including cubosomes.
Abstract: Lyotropic liquid crystalline nanostructured particles, such as cubosomes, have grown in popularity as drug delivery systems in the last few years These systems require steric stabilizers to maintain colloidal stability in an aqueous medium, with Pluronic®F127, a block copolymer, being the most commonly employed stabilizer However, in recent years, alternative, more effective stabilizers, as well as rationally designed systems with opportunities for further biofunctionalization have been reported The purpose of this chapter is to collate and collectively interpret studies in the field of steric stabilization of this important emerging class of nanoparticles for drug and medical imaging agent delivery
60 citations
TL;DR: In this article, two imidazolium-based surface active ionic liquids (SAILs) with photoresponsive cinnamate aromatic counterions were newly synthesized, and their self-assembly behaviors in aqueous solutions were systematically explored.
Abstract: Two imidazolium-based surface active ionic liquids (SAILs) with photoresponsive cinnamate aromatic counterions, viz. 1-dodecyl-3-methylimidazolium cinnamate ([C12mim][CA]) and 1-dodecyl-3-methylimidazolium para-hydroxy-cinnamate ([C12mim][PCA]), were newly synthesized, and their self-assembly behaviors in aqueous solutions were systematically explored. Results of surface tension and conductivity measurements show that both [C12mim][CA] and [C12mim][PCA] display a superior surface activity in aqueous solutions compared to the common imidazolium-based SAIL, 1-dodecyl-3-methylimidazolium bromide (C12mimBr), which implies the incorporation of cinnamate aromatic counterions can promote the micellar formation. Furthermore, [C12mim][CA] shows higher surface activity due to the higher hydrophobicity of its counterion in comparison to [C12mim][PCA] that has a hydroxyl group. Both hexagonal liquid-crystalline phase (H1) and cubic liquid-crystalline phase (V2) were constructed in the [C12mim][CA] aqueous solutions. In contrast, the [C12mim][PCA]/H2O system only exhibits a single hexagonal liquid-crystalline phase (H1) in a broad concentration region. These lyotropic liquid crystal (LLC) phases were comprehensively characterized by polarized optical microscopy (POM), small-angle X-ray scattering (SAXS), and rheometer. Investigation on the temperature-dependent self-assembly nanostructures demonstrates that the higher temperature leads to a looser arrangement. Under UV irradiation, trans-cis photoisomerization of the phenylalkene group results in inferior surface activity of the prepared SAILs in aqueous solution with higher cmc values. Moreover, UV light irradiation induces obvious change of the structural parameters without altering the LLC phases. This work is expected to enrich the investigations of phase behaviors formed in SAILs systems and receive particular attention due to their unique properties and potential applications in drug delivery, biochemistry, materials science, etc.
42 citations
TL;DR: A self-assembled lyotropic liquid crystal (LLC) system exhibiting dynamic and reversible polymorphism between two ordered structures in a closed system consisting of fully synthetic molecules is developed.
Abstract: A self-assembled lyotropic liquid crystal (LLC) system exhibiting dynamic and reversible polymorphism was developed using the synthetic cyclic ethynylhelicene oligomers cyclobis[(M)-D-n] (n = 4 and 6), in which two oligomer moieties are connected by two flexible linkers. The cyclic molecular structure was designed to control aggregation properties ranging from the molecular level to the macroscopic level. The cyclic oligomer changed its structure between random coils and an intramolecular homo-double helix induced by temperature and solvents. In the presence of pseudoenantiomeric acyclic oligomers, cyclobis[(M)-D-4] formed trimolecular complexes with a total molecular weight of over 10 000 Da containing two intermolecular hetero-double helices. The trimolecular complex formation predominated over bimolecular complex formation. The trimolecular complex self-assembled at high concentrations and formed LLCs composed of anisotropically aligned fibers. The result is in contrast to acyclic systems, which form g...
37 citations
TL;DR: Self-assembled microstructures of biocompatible and biodegradable tetraglycerol lauryl ether (C12G4) nonionic surfactant in an aqueous solvent system are described, demonstrating the greater thermal stability of the self-assembled mesophases.
Abstract: Amphiphiles, molecules that possess both hydrophilic and hydrophobic moieties, are architecturally simple molecules that can spontaneously self-assemble into complex hierarchical structures from lower to higher dimensions either in the bulk phase or at an interface. Recent developments in multifunctional nanostructure design using the advanced concept of nanoarchitectonics utilize this simple process of assembly. Amphiphilic self-assemblies involving lipids or proteins mimic the structure of biological systems, thus highlighting the necessity of a fundamental physical understanding of amphiphilic self-assembly towards a realization of the complex mechanisms operating in nature. Herein, we describe self-assembled microstructures of biocompatible and biodegradable tetraglycerol lauryl ether (C12G4) nonionic surfactant in an aqueous solvent system. Temperature-composition analyses of equilibrium phases identified by using small-angle x-ray scattering (SAXS) provide strong evidence of various spontaneously selfassembled mesostructures, such as normal micelles (Wm), hexagonal liquid crystal (H1), and reverse micelles (Om). In contrast to conventional poly(oxyethylene) nonionic surfactants, C12G4 did not exhibit the clouding phenomenon at higher temperatures (phase separation was not observed up to 100 °C), demonstrating the greater thermal stability of the self-assembled mesophases. Generalized indirect Fourier transformation (GIFT) evaluation of the SAXS data confirmed the formation of core–shell–type spherical micelles with a maximum dimension ca. 8.7nm. The shape and size of the C12G4 micelles remained apparently unchanged over a wide range of concentrations (up to 20%), but intermicellar interactions increased and could be described by the Percus–Yevick (PY) theory (after Carnahan and Starling), which provides a very accurate analytical expression for the osmotic pressure of a monodisperse hard sphere.
34 citations
01 Jan 2015
TL;DR: Two imidazolium-based surface active ionic liquids with photoresponsive cinnamate aromatic counterions were newly synthesized, and their self-assembly behaviors in aqueous solutions were systematically explored to enrich the investigations of phase behaviors formed in SAILs systems.
Abstract: Two imidazolium-based surface active ionic liquids (SAILs) with photoresponsive cinnamate aromatic counterions, viz. 1-dodecyl-3- methylimidazolium cinnamate ((C12mim)(CA)) and 1-dodecyl-3-methylimi- dazolium para-hydroxy-cinnamate ((C12mim)(PCA)), were newly synthe- sized, and their self-assembly behaviors in aqueous solutions were systemati- cally explored. Results of surface tension and conductivity measurements show that both (C12mim)(CA) and (C12mim)(PCA) display a superior surface activity in aqueous solutions compared to the common imidazolium-based SAIL, 1-dodecyl-3-methylimidazolium bromide (C12mimBr), which implies the incorporation of cinnamate aromatic counterions can promote the micellar formation. Furthermore, (C12mim)(CA) shows higher surface activity due to the higher hydrophobicity of its counterion in comparison to (C12mim)(PCA) that has a hydroxyl group. Both hexagonal liquid-crystalline phase (H1) and cubic liquid-crystalline phase (V2) were constructed in the (C12mim)(CA) aqueous solutions. In contrast, the (C12mim)(PCA)/ H2O system only exhibits a single hexagonal liquid-crystalline phase (H1) in a broad concentration region. These lyotropic liquid crystal (LLC) phases were comprehensively characterized by polarized optical microscopy (POM), small-angle X-ray scattering (SAXS), and rheometer. Investigation on the temperature-dependent self-assembly nanostructures demonstrates that the higher temperature leads to a looser arrangement. Under UV irradiation, trans−cis photoisomerization of the phenylalkene group results in inferior surface activity of the prepared SAILs in aqueous solution with higher cmc values. Moreover, UV light irradiation induces obvious change of the structural parameters without altering the LLC phases. This work is expected to enrich the investigations of phase behaviors formed in SAILs systems and receive particular attention due to their unique properties and potential applications in drug delivery, biochemistry, materials science, etc.
TL;DR: It is demonstrated herein that the lyotropic self-assembly behaviors of gemini dicarboxylates sensitively depend on the linker length, whereby odd-carbon linkers stabilize the double gyroid network LLC over unprecedented amphiphile concentration windows up to ∼45 wt % wide between T ≈ 22-80 °C.
Abstract: Network-phase lyotropic liquid crystals (LLCs) derived from the water-directed self-assembly of small molecule amphiphiles comprise a useful class of soft nanomaterials, with wide-ranging applications in structural biology and membrane science. However, few known surfactants enable access to these mesophases over wide temperature and amphiphile concentration phase windows. Recent studies have demonstrated that gemini (“twin tail”) dicarboxylate surfactants, in which alkyl carboxylates are covalently linked near the headgroups by a hydrophobic bridge, exhibit increased propensities to form double gyroid network phase LLCs. We demonstrate herein that the lyotropic self-assembly behaviors of gemini dicarboxylates sensitively depend on the linker length, whereby odd-carbon linkers stabilize the double gyroid network LLC over unprecedented amphiphile concentration windows up to ∼45 wt % wide between T ≈ 22–80 °C. These self-assembly phenomena, which arise from the linker length-dependent preferred molecular co...
TL;DR: Single-step and sequential light-triggered release and retention of the embedded dye molecules are demonstrated, thereby achieving exquisite temporal, spatial, and dosage control of the release, opening up the possibility of using such lipidic biomaterials as effective matrices in therapy, when a continuous release of active drugs might be toxic.
Abstract: Here, we present the design and assembly of a new light-responsive functional lyotropic liquid crystal system using host–guest lipidic mesophases (LMPs). Light as an external stimulus has many advantages in comparison to other stimuli: it is milder than acids or bases, and variation of intensity and duration can provide a high level of pharmacological control. The LMPs are composed of monoolein (MO) and oleic acid (OA) as host lipids and a small amount of a judiciously synthesized lipid bearing an azobenzene photoactive unit as a guest. While preserving the structure and stability of the host lipidic aggregates, the guest lipids render them specific functionalities. Single-step and sequential light-triggered release and retention of the embedded dye molecules are demonstrated, thereby achieving exquisite temporal, spatial, and dosage control of the release, opening up the possibility of using such lipidic biomaterials as effective matrices in therapy, when a continuous release of active drugs might be toxic.
TL;DR: A review of hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, can be found in this paper, where a typology of these materials is introduced.
Abstract: Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.
TL;DR: Both the phase behavior and the rheological properties of the LC phases support the hypothesis that gelled lyotropic liquid crystals are orthogonal self-assembled systems, and freeze-fracture electron microscopy (FFEM) seems to indicate an influence of the gel network on the structure of the Lα phase and vice versa.
Abstract: In our previous work we were able to prove that gelled bicontinuous microemulsions are a novel type of orthogonal self-assembled system. The study at hand aims at complementing our previous work by answering the question of whether gelled lyotropic liquid crystals are also orthogonal self-assembled systems. For this purpose we studied the same system, namely, water–n-decane/12-hydroxyoctadecanoic acid (12-HOA)–n-decyl tetraoxyethylene glycol ether (C10E4). The phase boundaries of the nongelled and the gelled lyotropic liquid crystals were determined visually and with 2H NMR spectroscopy. Oscillating shear measurements revealed that the absolute values of the storage and loss moduli of the gelled liquid crystalline (LC) phases do not differ very much from those of the binary organogel. While both the phase behavior and the rheological properties of the LC phases support the hypothesis that gelled lyotropic liquid crystals are orthogonal self-assembled systems, freeze–fracture electron microscopy (FFEM) see...
TL;DR: In this paper, the rheological and microstructural shear response of a mixture of polyvinylpyrrolidone (PVP) coated silver nanowires and nanoparticle aggregates (Ag) dispersed in ethylene glycol (EG) or water (H2O).
Abstract: We report the rheological and microstructural shear response of a mixture of polyvinylpyrrolidone (PVP) coated silver nanowires and nanoparticle aggregates (Ag) dispersed in ethylene glycol (EG) or water (H2O). Biphasic and liquid crystalline dispersions exhibited rheological characteristics similar to those of lyotropic liquid crystalline polymers (LCPs). The viscosity versus concentration curve for Ag-EG dispersions showed a viscosity minimum at a silver concentration between 2.2 vol.% and 2.9 vol.%; this is indicative of the transition to an entirely liquid crystalline phase. The rheology results were consistent with optical microscopy observations that at 2.9 vol.% the sample was entirely birefringent; this is another indication of liquid crystalline phase formation. Shear had a significant effect on the microstructure of the dispersions and dried coatings. Depending on the shear rate, worm or shear banding Structures were observed.
TL;DR: The secondary structure of the Ag43 proteins was affected by the hydrophobic thickness and physicochemical properties of the lipid bilayer and the water channel diameter of the cubic phase, which could potentially affect membrane protein function.
Abstract: Lipidic bicontinuous cubic mesophases with encapsulated amphiphilic proteins are widely used in a range of biological and biomedical applications, including in meso crystallization, as drug delivery vehicles for therapeutic proteins, and as biosensors and biofuel cells. However, the effect of amphiphilic protein encapsulation on the cubic phase nanostructure is not well-understood. In this study, we illustrate the effect of incorporating the bacterial amphiphilic membrane protein Ag43, and its individual hydrophobic β(43) and hydrophilic α(43) domains, in bicontinuous cubic mesophases. For the monoolein, monoalmitolein, and phytantriol cubic phases with and without 8% w/w cholesterol, the effect of the full length amphiphilic protein Ag43 on the cubic phase nanostructure was more significant than the sum of the individual hydrophobic β(43) and hydrophilic α(43) domains. Several factors were found to potentially influence the impact of the hydrophobic β(43) domain on the cubic phase internal nanostructure. These include the size of the hydrophobic β(43) domain relative to the thickness of the lipid bilayer, as well as its charge and diameter. The size of the hydrophilic α(43) domain relative to the water channel radius of the cubic mesophase was also found to be important. The secondary structure of the Ag43 proteins was affected by the hydrophobic thickness and physicochemical properties of the lipid bilayer and the water channel diameter of the cubic phase. Such structural changes may be small but could potentially affect membrane protein function.
TL;DR: In this paper, Bicontinuous and water-in-diesel microemulsions were formulated using single nonionic alkyl poly glycol ethers combined with hydrophilic alcohol ethoxylates.
Abstract: Bicontinuous and water-in-diesel microemulsions were formulated using single nonionic alkyl poly glycol ethers combined with hydrophilic alcohol ethoxylates. The phase behavior at temperatures ranging from 0°C to 50°C was investigated. Visual inspection as well as cross-polarizers were used to detect anisotropy. The fish phase diagrams were determined. The presence of the hydrophilic alcohol ethoxylates was necessary to initiate both types of microemulsions. Increasing the hydrophobic chain length of the surfactant led to a wider range of temperature stability at lower surfactant concentration. Meanwhile, increasing the ethylene oxide units in the headgroup by two units led to a phase diagram that is dominated by lyotropic liquid crystal. The formulated water in diesel microemulsions were tested experimentally in a 4-cylinder diesel engine. From this it is observed that the emissions of NOx, soot, and CO2 were reduced substantially compared to neat diesel, while for the CO the reduction occurs just at low...
TL;DR: It is pointed out that the unlike relative configuration of the two surfactants influences their chiral recognition ability as well as the fashion in which chirality is expressed at the supramolecular level by controlling the molecular organization in both micellar aggregates and surfactant/bilirubin heteroaggregates.
Abstract: Novel diastereomeric anionic amphiphiles based on the rigid cyclobutane β-amino acid scaffold have been synthesized and deeply investigated with the aim of generating new functional supramolecular architectures on the basis of the rational design of original amphiphilic molecules and the control of their self-assembly. The main interest has been focused on the effect that cis/trans stereochemistry exerts on their molecular organization and recognition. In diluted solutions, the relative stereochemistry mainly influences the headgroup solvation and anionic-charge stabilization, i.e., better stabilized in the cis diastereoisomer due to intramolecular hydrogen-bonding and/or charge-dipole interactions. This provokes differences in their physicochemical behavior (pKa, cmc, conductivity) as well as in the structural parameters of the spherical micelles formed. Although both diastereoisomers form fibers that evolve with time from the spherical micelles, they display markedly different morphology and kinetics of formation. In the lyotropic liquid crystal domain, the greatest differences are observed at the highest concentrations and can be ascribed to different hydrogen-bonding and molecular packing imposed by the stereochemical constraints. Remarkably, the spherical micelles of the two anionic surfactants show dramatically diverse enantioselection ability for bilirubin enantiomers. In addition, both the surfactants form heteroaggregates with bilirubin at submicellar concentrations but with a different expression of supramolecular chirality. This points out that the unlike relative configuration of the two surfactants influences their chiral recognition ability as well as the fashion in which chirality is expressed at the supramolecular level by controlling the molecular organization in both micellar aggregates and surfactant/bilirubin heteroaggregates. All these differential features can be appropriate and useful for the design and development of new soft materials with predictable and tunable properties and reveal the cyclobutane motif as a valuable scaffold for the preparation of new amphiphiles.
TL;DR: A novel polymerizable ionic liquid based LLC, 1-hexadecyl-3-methylimidazolium acrylate (C16mimAcr), where the acrylated anion acts as the polymerizable moiety, which has more complex phase behaviour compared to the C16mIMCl system.
Abstract: The development of new polymerizable lyotropic liquid crystals (LLCs) utilizing charged amphiphilic molecules such as those based on long chain imidazolium compounds, is a relatively new design direction for producing robust membranes with controllable nano-structures. Here we have developed a novel polymerizable ionic liquid based LLC, 1-hexadecyl-3-methylimidazolium acrylate (C16mimAcr), where the acrylate anion acts as the polymerizable moiety. The phase behaviour of the C16mimAcr upon the addition of water was characterized using small and wide angle X-ray scatterings, differential scanning calorimetry and polarized optical microscopy. We compare the phase behaviour of this new polymerizable LLC to that of the well known LLC chloride analogue, 1-hexadecyl-3-methylimidazolium chloride (C16mimCl). We find that the C16mimAcr system has a more complex phase behaviour compared to the C16mimCl system. Additional lyotropic liquid crystalline mesophases such as hexagonal phase (H1) and discontinuous cubic phase (I1) are observed at 20 °C for the acrylate system at 50 and 65 wt% water respectively. The appearance of the hexagonal phase (H1) and discontinuous cubic phase (I1) for the acrylate system is likely due to the strong hydrating nature of the acrylate anion, which increases the head group area. The formation of these additional mesophases seen for the acrylate system, especially the hexagonal phase (H1), coupled with the polymerization functionality offers great potential in the design of advanced membrane materials with selective and anisotropic transport properties.
TL;DR: In this paper, the effect of Hofmeister anions on the existence of biaxial nematic phase and uniaxia-to-baixial phase transition was investigated.
Abstract: Lyotropic mixtures including different sodium salts of Hofmeister anions were studied in order to investigate the effect of these anions on the existence of biaxial nematic phase and on the uniaxial to biaxial phase transitions For this purpose, these sodium salts were added singly into different mixtures of dodecyltrimethylammonium bromide (DDTMABr)/1-dodecanol/water, keeping the relative molar concentration of all the constituents constant The uniaxial to biaxial phase transitions were determined from the temperature dependence of the birefringences by laser conoscopy Micellar shape anisometry and average micellar volume were evaluated from small-angle X-ray scattering measurements The results indicated that the Hofmeister anions were bounded to the head groups of DDTMABr molecules at the micelles’ surfaces, which significantly affect the different orientational fluctuations responsible for the formation of different nematic phases, biaxial phase domains and uniaxial to biaxial phase transition temp
TL;DR: The hydroxyl group in the spacer of a cationic Gemini surfactant caused dramatic changes of the phase behaviors in a protic ionic liquid (EAN), and the hexagonal phases formed with 12-3OH-12 exhibited lower viscoelasticity and thermostability than those observed in 12- 3-12/EAN system.
Abstract: The hydroxyl group in the spacer of a cationic Gemini surfactant (12-3OH-12) caused dramatic changes of the phase behaviors in a protic ionic liquid (EAN). Here, the effects of the hydroxyl group on micellization and lyotropic liquid crystal formation were investigated through the surface tension, small-angle X-ray scattering, polarized optical microscopy, and rheological measurements. With the hydroxyl group in the spacer, the critical micellization concentration of 12-3OH-12 was found to be lower than that of the homologue without hydroxyl (12-3-12) and the 12-3OH-12 molecules packed more densely at the air/EAN interface. It was then interesting to observe a coexistence of two separated phases at wide concentration and temperature ranges in this 12-3OH-12/EAN system. Such a micellar phase separation was rarely observed in the ionic surfactant binary system. With the increase of surfactant concentration, the reverse hexagonal and bicontinuous cubic phases appeared in sequence, whereas only a reverse hexa...
TL;DR: The findings reported herein will not only present an easy way to design novel luminescent lanthanide β-diketonate soft materials, but also provide a useful reference to better understand the LLC phase structure effects on the luminescence properties.
Abstract: Luminescent materials from europium β-diketonate complex in ionic liquids (ILs) could achieve enhanced luminescence efficiencies and photostabilities. However, the question of how to provide a feasible and environmentally-friendly way to distribute these lanthanide complexes uniformly and stably within IL-based matrix remains a significant challenge. Here, a soft luminescent material from IL-mediated lyotropic liquid crystals (LLCs) doped with [Bmim][Eu(TTA)4] (Bmim = 1-butyl-3-methyl imidazolium, TTA = 2-thenoyltrifluoroacetone) has been constructed by a convenient self-assembling method. The hexagonal or lamellar LLC phases could be identified by small-angle X-ray scattering (SAXS) measurements. All LLC samples exhibited intense red luminescence upon exposure to ultraviolet radiation. The good dispersibility of the complexes in LLC matrices and their good photostability (as in ILs) was verified by steady-state luminescence spectroscopy. The isolated and unique characteristics of the microenvironment within the LLCs were noteworthy to decrease the nonradiative deactivation of the excited states, thereby allowing more efficient energy transfer and longer lifetimes than those in pure complex or IL solutions. Both the luminescent property and the stability of the LLC materials were different in different phase structures, the complexes behaving better in the lamellar phase than in the hexagonal one. The findings reported herein will not only present an easy way to design novel luminescent lanthanide β-diketonate soft materials, but also provide a useful reference to better understand the LLC phase structure effects on the luminescence properties.
TL;DR: Schiff-base macrocycles that combine keto-enamine and enol-imine tautomers within the same ring were synthesized and characterized and unexpectedly form a lyotropic liquid crystal in organic solvents such as chloroform and toluene.
TL;DR: In this paper, a system was designed with the desired physical and rheology properties for cosmetic and pharmaceutical applications based on structured reverse lyotropic liquid crystals (LLC) as oleogels.
Abstract: In the course of our studies on structured reverse lyotropic liquid crystals (LLC) as oleogels, a system was designed with the desired physical and rheology properties for cosmetic and pharmaceutical applications. The aqueous phase was partially replaced by glycerol to minimize bacteriological problems and obtain specific rheology characteristics. The constructed phase diagrams are based on ternary mixtures of glycerol monooleate (GMO), decane, water, and glycerol. The main lyotropic mesophase obtained in this study was reverse hexagonal derived from dilution line 8:2 (72 wt% GMO and 18 wt% decane) and 10 wt% water; or water:glycerol (wt ratios 3:1 and 1:1) mixture. It was found that heat-cool fluctuation caused formation of new pseudo-equilibrium structures with mesomorphic transformations to more fluid and less ordered mesostructures. Replacing up to 50 wt% of the water by glycerol significantly increases the gel phase region in the phase diagram, meaning more structural compositional options. The structural parameters were determined using cross-polarized light microscopy (CPLM), differential scanning calorimeter (DSC), powder X-ray diffraction (PXRD), and small angle X-ray scattering (SAXS). Rheological measurements revealed viscoelastic properties of lyotropic liquid crystals with a decrease in the elasticity (G′), plasticity (G″), and complex viscosity (η*), as a function of increasing the glycerol content.
TL;DR: In this paper, the self-assembly of fluororous protic ionic liquids (FPILs) was shown to transition from a low water content L 3 sponge structure in EOAF, to a L α lamellar mesophase and then to dispersed lamlar vesicles.
TL;DR: In this article, the effects of silver nitrate and urocanic acid on multibilayer structures of hydrated phospholipids have been studied by small-angle X-ray scattering and differential scanning calorimetry (DSC).
Abstract: Multibilayer structures of hydrated phospholipids, often considered as model biological membranes, are, from the physical viewpoint, lyotropic liquid crystalline systems undergoing temperature-induced mesomorphic phase transitions. Effects of silver nitrate and urocanic acid on lyotropic phase states of hydrated L-α-dipalmitoylphosphatidylcholine (DPPC) have been studied by small-angle X-ray scattering and differential scanning calorimetry (DSC). Both methods show increase of the main phase-transition temperature (Tm) of hydrated DPPC upon introduction of AgNO3 or urocanic acid, decrease of pre-transition temperature (Tp) in the presence of urocanic acid and its increase in the presence of AgNO3. Thus, urocanic acid widened the ripple-phase temperature region. Silver nitrate caused the appearance of an additional high-temperature peak on DSC thermograms, evidencing phase separation in the system. Both agents caused minor effects on DPPC lipid bilayer repeat distance (D) in gel phase, but resulted in notic...
TL;DR: In this paper, the formation of helical superstructures in cholesteric, Twist Grain Boundary and ferroelectric phases is discussed, as well as the occurrence of novel thermodynamic phases.
Abstract: The introduction of chirality, i.e., the lack of mirror symmetry, has a profound effect on liquid crystals, not only on the molecular scale but also on the supermolecular scale and phase. I review these effects, which are related to the formation of supermolecular helicity, the occurrence of novel thermodynamic phases, as well as electro-optic effects which can only be observed in chiral liquid crystalline materials. In particular, I will discuss the formation of helical superstructures in cholesteric, Twist Grain Boundary and ferroelectric phases. As examples for the occurrence of novel phases the Blue Phases and Twist Grain Boundary phases are introduced. Chirality related effects are demonstrated through the occurrence of ferroelectricity in both thermotropic as well as lyotropic liquid crystals. Lack of mirror symmetry is also discussed briefly for some biopolymers such as cellulose and DNA, together with its influence on liquid crystalline behavior.
TL;DR: Novel organogel based lyotropic liquid crystals (LLC) were prepared and investigated as controlled release matrices and showed good antimicrobial efficacy against Escherichia coli and biocompatibility against human keratinocytes.
TL;DR: In this paper, the authors highlight some of the recent developments in the emerging field of hybrid amphiphiles, focusing on systems with at least one inorganic constituent, depending on if the inorganic entity is molecular or has particle character.
Abstract: Amphiphiles and surfactants are indispensable compounds in industry, scientific research and everyday life, such as emulsification agents, detergents, etc. The vast majority of currently used amiphiphiles are organic in nature, and are composed of two molecular parts joined together, one hydrophilic and one hydrophobic. The current article highlights some of the recent developments in the emerging field of hybrid amphiphiles, focusing on systems with at least one inorganic constituent. Different classes of amphiphiles can be defined, depending on if the inorganic entity is molecular or has particle character, and depending on the strength of interaction between the inorganic and organic phase. It is seen that in addition to typical amphiphilic properties, most importantly the formation of self-assembled structures like micelles or lyotropic liquid crystals, the hybrid amphiphiles exhibit additional, functional features like special magnetic or catalytic properties. Ultimately, systemic features can be observed, leading to the emergence of new properties which none of the constituents of hybrid amphiphile could have on its own.