Microstructure and rheological properties of liquid crystallines formed in Brij 97/water/IPM system

The phase diagram of Brij 97/water/IPM systems was determined at 25 degrees C. Rich liquid crystalline phases including Lalpha, H1, and cubic Fd3m phases were identified by means of small angle X-ray scattering (SAXS). Microstructure transitions of liquid crystals with changes in surfactant concentration and oil content are explained qualitatively by the surfactant packing parameter (vL/aSlc). Dynamic rheological results indicate that all three kinds of liquid crystals investigated show high elasticity. The lamellar, Lalpha, phases formed in Brij 97/water with two different oils, oleic acid and geraniol, were also studied in comparison with those of Brij 97/water/IPM systems. The strength of the network of lamellar phases formed in Brij 97/water/oleic acid and Brij 97/water/geraniol systems are appreciably stronger than for Brij 97/water/IPM systems, indicated by the smaller area of surfactant molecules at the interface and the higher moduli (G' and G').     

Hexagonal liquid crystalline phases formed in ternary systems of Brij 97-water-ionic liquids

Phase diagrams of two ionic liquids: hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate (bmim-PF(6)) and relatively hydrophilic 1-butyl-3-methylimidazolium tetrafluoroborate (bmim-BF(4)) in aqueous solutions of Brij 97 were determined at 25 degrees C. Two hexagonal liquid crystalline phases formed in bmim-PF(6)- and bmim-BF(4)-containing ternary systems were investigated by means of small-angle X-ray scattering (SAXS) and rheological techniques, with comparison of composition and temperature effects. From analysis of the SAXS data, bmim-PF(6) is dominantly penetrated between the oxyethylene chains of surfactant molecules, whereas bmim-BF(4) is mainly located in the water layer of hexagonal phases. The strength of the network of hexagonal phase formed in the Brij 97/water/bmim-BF(4) system is appreciably stronger than that of the Brij 97/water/bmim-PF(6) system, indicated by the smaller area of the surfactant molecule at the interface and the higher moduli (G', G' '). Temperature has a converse effect on the lattice parameters of the two hexagonal phases.     

Study on the formation and rheological properties of sucrose stearate lamellar liquid crystals

The phase diagrams of S1570–Brij 97/oleic acid/water system at two different S1570/Brij 97 mass ratios of 1/1 (system S) and 7/3 (system P) were determined at 37°C, respectively. The microstructures and rheological properties of liquid crystals at constant surfactants/water mass ratio of 1/1 were studied with increase in oil content. Small-angle x-ray scattering measurements showed that system S exhibited a typical lamellar liquid crystals and the repeat distance (d) decreased as oil content increased. While for system P, two couples of scattering peaks were observed when oil content reached 28 wt%. This indicated that adding oil content may give rise to a multilamellar structures in the higher S1570/Brij 97 mass ratio system. The rheological tests indicated that a transition from elastic gel-like properties to viscoelastic liquid-like properties appeared in both system S and P when oil content reached 20 wt%, corresponding to the polarizing optical microscopy textures changing from oily streak to cruciate flower. This supplies a way to adjust structure, rheological properties, and even phase transition by altering the S1570/Brij 97 mass ratio and oleic acid content in system.     

Nonionic diethanolamide amphiphiles with unsaturated C18 hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behavior

The neat and lyotropic liquid crystalline phase behavior of three nonionic diethanolamide amphiphiles with C18 hydrocarbon chains containing one, two or three unsaturated bonds has been examined. This has allowed the effect of degree of unsaturation on the phase behavior of diethanolamide amphiphiles to be investigated. Neat linoleoyl and linolenoyl diethanolamide undergo a transition from a glassy liquid crystal to a liquid crystal at ～-85 °C, while neat oleoyl diethanolamide undergoes a transition at ～-60 °C to a liquid crystalline material before re-crystallizing at -34 °C. Oleoyl diethanolamide then undergoes a third transition from a crystalline phase to a smectic liquid crystalline phase at ～5 °C. In the absence of water, the transition temperature from a smectic liquid crystal to an isotropic liquid decreases with increasing unsaturation. The addition of water results in the formation of a lamellar phase (L(α)) for all three amphiphiles. The lamellar phase is stable under excess water conditions up to temperatures of at least 70 °C. Approximate partial binary amphiphile-water phase diagrams generated for the three unsaturated C18 amphiphiles indicate that the excess water point for each amphiphile occurs at ～60% (w/w) amphiphile.     

Lyotropic Liquid Crystals Formed by Brij 97/PEO‐PPO‐PEO Mixtures

The phase diagrams of Brij 97/(PEO)_m(PPO)_n(PEO)_m/water/IPM quaternary systems (A L‐64: m=13, n=30; A L‐62: m=7, n=32; A L‐61: m=3.5, n=31) were determined at 25°C. The liquid crystalline phases (lamellar L_αand hexagonal H₁) were investigated by means of small angle x‐ray scattering (SAXS) and rheological techniques, with comparison of composition and component effects. The lamellar phases formed in Brij 97/A L‐64 and Brij 97/A L‐62 systems array more orderly than that of Brij 97/A L‐61 system, indicated by the stronger intensity of the second reflection peak in the SAXS patterns and the higher moduli (G′ and G″) in the dynamic rheograms. In Brij 97/A L‐64/water/IPM system, all L_α phases exhibit elastic rheograms, moreover the viscous property get increased with increase in water content. On the other hand, with this change, the H₁ phases show Maxwell and gel‐like rheograms in order, in which the latter shows mechanical and relaxation spectra typical of highly structured materials.     

Nonionic diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behaviour

The thermotropic and lyotropic liquid crystalline phase behaviour of a series of diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains (geranoyl, H-farnesoyl, and phytanoyl) has been investigated. When neat, both H-farnesoyl and phytanoyl diethanolamide form a smectic liquid crystalline structure at sub-zero temperatures. In addition, all three diethanolamides exhibit a glass transition temperature at around -73 °C. Geranoyl diethanolamide forms a lamellar crystalline phase with a lattice parameter of 17.4 ? following long term storage accompanied by the loss of the glass transition. In the presence of water, H-farnesoyl and phytanoyl diethanolamide form lyotropic liquid crystalline phases, whilst geranoyl diethanolamide forms an L(2) phase. H-farnesoyl diethanolamide forms a fluid lamellar phase (L(α)) at room temperature and up to ～ 40 °C. Phytanoyl diethanolamide displays a rich mesomorphism forming the inverse diamond (Q(II)(D)) and gyroid (Q(II)(G)) bicontinuous cubic phases in addition to an L(α) phase.     

Lamellar Liquid Crystals of Brij 97 Aqueous Solutions Containing Different Additives

Lamellar liquid crystals of Brij 97 aqueous solutions were investigated by means of rheological techniques and SAXS at 25 °C, in the presence of various additives including isopropyl myristate, oleic acid, ionic liquid bmim-PF₆ and bmim-BF₄. The lamellar phases show high elasticity as indicated by their mechanical and discrete relaxation spectra, which is expected to be an advantage when they are used as drug delivery vehicles. It is noted that in comparison with other systems, the lamellar phase formed in the Brij 97/water/IPM system has the lowest storage and loss moduli, implying that it has a weak network strength and less stable internal structure. The Brij 97/water/oleic acid system is the most shear resistance, whereas the Brij 97/water/bmim-PF₆ system exhibits fluid-like viscoelastic properties to some extent. These differences are analyzed through SAXS data for the different location of the additive in the lamellar phase.     

Rheological properties of lyotropic liquid crystals encapsulating curcumin

This study constructed new curcumin-loaded lyotropic liquid crystals containing pharmaceutically accepted oil, and ethyl oleate (EtOL). Three liquid crystalline phases including lamellar, hexagonal, and cubic phases were identified by means of the polarized optical microscopy and rheology method. By analyzing the shear viscosity (η_0.1), the viscosity of curcumin-liquid crystals is smaller than those without curcumin. Dynamic rheological results show that: Dissolved curcumin in EtOL can make the elastic modulus of hexagonal and cubic phase increase compared with that without curcumin, while the elastic modulus of lamellar phase decreases. Dissolved curcumin in Brij 97 can lead to the decreasing of the elastic modulus for cubic and lamellar phases, whereas it has little influence on hexagonal phase. When the curcumin is solubilized in both EtOL and Brij 97, the elastic modus of hexagonal phase increase, the elastic modus of lamellar and cubic phases decrease compared with that without curcumin. Furthermore, three temperature turning points were identified by the change in the slope of tanδ (G″/G′) for curcumin-hexagonal liquid crystal. These studies might be a help to study the storage of drug carrier and in vitro release properties of lyotropic liquid crystals containing curcumin.     

Phase equilibria and critical phenomena in the cesium nitrate–water–pyridine ternary system

The solubilities of components, phase equilibria, and critical phenomena in the cesium nitrate–water–pyridine ternary system are studied in the 5–100°C temperature range by the visual–polythermal method. Cesium nitrate is found to exhibit a salting-out effect at temperatures above 79.9°C causing phase separation in homogeneous water–pyridine solutions. The temperature of formation of the critical monotectic tie line (79.9°C) and the compositions of solutions corresponding to the liquid–liquid critical points at three temperatures are determined. The pyridine distribution coefficients between the aqueous and organic phases of the monotectic state at 85.0, 90.0, and 100.0°C are calculated. Their values demonstrate that salting-out of pyridine from aqueous solutions by cesium nitrate increases at higher temperatures. The plotted isotherms of phase diagrams confirm the fragment of the scheme of topological transformation of the phase diagrams of salt–binary solvent ternary systems with salting-in and salting-out phenomena.     

Many protic ionic liquids mediate hydrocarbon-solvent interactions and promote amphiphile self-assembly

A large number of protic ionic liquids (PILs) have been found to mediate solvent-hydrocarbon interactions and promote amphiphile self-assembly. Hexagonal, cubic, and lamellar lyotropic liquid crystalline phases were observed in PIL-hexadecyltrimethylammonium bromide systems. The driving force for the formation of the self-assembled aggregate structures has been attributed to an entropic contribution to the free energy of association, analogous to the hydrophobic effect in water. The specific aggregate structures formed depend upon the cationic and anionic components of the PIL and their interactions with the amphiphiles.     

Lyotropic liquid crystalline phases formed by phyosterol ethoxylates in room-temperature ionic liquids

The phase behaviors of four phytosterol ethoxylates surfactants (BPS-n, n = 5, 10, 20, and 30) with different oxyethylene units in room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄), have been studied. The polarized optical microscopy and small-angle X-ray scattering techniques are used to characterize the phase structures of these binary systems at 25 °C. The structure and ordering of the liquid crystalline (LC) phases in such BPS-n/[Bmim]BF₄ systems are found to be influenced by BPS-n concentration and the temperature. Due to the bulky and rigid cholesterol group, the phytosterol ethoxylates surfactants exhibit different properties and interaction mechanism from the conventional C_nEO_m type nonionic surfactant systems. The rheological measurements indicate a highly viscoelastic nature of these lyotropic LC phases and disclose a lamellar phase characteristic with a rather strong rigidity at high surfactant concentrations. The control experiment with Brij 97(polyoxyethylene (10) oleyl ether)/[Bmim]BF₄ system and the FTIR measurements help to recognize that the solvophobic interaction combining with the hydrogen bonding are the main driving forces for the LC phases formation.     

Amphotropic liquid-crystalline behaviour of glycolipids in amino acid ionic liquids

We examined lyotropic liquid-crystalline behaviour of glycolipids (GLs) with a normal alkyl chain or a diacetylene-functionalised alkyl chain in several amino acid ionic liquids (AAILs). It was found that the mixtures of GL and AAIL form various nanosegregated liquid-crystalline phases, such as smectic, bicontinuous cubic and hexagonal columnar phases, depending on the two-component ratio and AAIL species. The observed liquid-crystalline behaviours were summarised as phase diagrams. It is noteworthy that the employment of amino acid anions with superior hydrogen-bonding ability, such as aspartic and glutamic acid anions, gives a phase diagram with a wide liquid-crystalline region. Comparing with a phase diagram obtained for the GL/water mixtures, we gained insights on the similarity/dissimilarity between water and AAILs as self-organisation media of amphiphiles. For the diacetylene-functionalised molecule, UV irradiation was carried out to progress polymerisation. It is of interest that the polymerisation reaction progressed when the glycolipid formed a smectic phase in an AAIL while a reaction progress was not found when it formed a bicontinuous cubic phase in another AAIL. We believe that AAILs have a great potential to be a liquid media not only for amphiphiles but for various functional materials, such as polymers and colloids, to form novel assemblies.     

Origin of lyotropic liquid crystalline mesophase formation and liquid crystalline to mesostructured solid transformation in the metal nitrate salt-surfactant systems

The zinc nitrate salt acts as a solvent in the ZnX-C(12)EO(10) (ZnX is [Zn(H(2)O)(6)](NO(3))(2) and C(12)EO(10) is C(12)H(25)(OCH(2)CH(2))(10)OH) lyotropic liquid crystalline (LLC) mesophase with a drastic dropping on the melting point of ZnX. The salt-surfactant LLC mesophase is stable down to -52 °C and undergoes a phase change into a solid mesostructured salt upon cooling below -52 °C; no phase separation is observed down to -190 °C. The ZnX-C(12)EO(10) mesophase displays a usual phase behavior with an increasing concentration of the solvent (ZnX) in the media with an order of bicontinuous cubic(V(1))-2D hexagonal(H(1))--a mixture of 2D hexagonal and micelle cubic(H(1) + I)-micelle cubic(I)-micelle(L(1)) phases. The phase behaviors, specifically at low temperatures, and the first phase diagram of the ZnX-C(12)EO(10) system was investigated using polarized optical microscopy (POM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), and Raman techniques and conductivity measurements.     

Phase behavior of 1-alkylpyridinium octane-1-sulfonates. effect of the 1-alkylpyridinium counterion size

The temperature-versus-composition phase diagrams of eight different 1-alkylpyridinium octane-1-sulfonates (APOSs) in water were studied by 1H NMR, 2H NMR, pulsed gradient spin-echo NMR, small-angle X-ray diffraction, differential scanning calorimetry, surface tension and conductivity measurements, and polarizing microscopy. The number of carbons (n(c)) in the hydrocarbon chain of the pyridinium counterions was varied from n(c) = 1 to n(c) = 8 to study how the phase behavior of the APOS/2H2O systems was affected by a change in the chain length of the counterion. The sodium octane-1-sulfonate (NaOS)/water system was used as a reference. This system formed an isotropic micellar solution (L1) phase and a normal hexagonal (H(I)) phase. All APOSs were readily soluble in water and formed L1 phases. The surface tension above the critical micelle concentration for n(c) between 1 and 3 was higher than that for NaOS, and it decreased steadily for the different APOSs with increasing chain length. The area per molecule at the air/solution interfaces was rather constant at 68 A2 for n(c) between 1 and 7. For 1-octylpyridinium octane-1-sulfonate (OPOS), it was about 5 A2 smaller, which was just outside the estimated error. However, the smallest area was obtained for NaOS. At higher surfactant concentrations, liquid crystalline phases formed. Both cubic and H(I) phases were found for n(c) = 1 and 2, while for n(c) between 3 and 5 only an H(I) phase was observed. H(I) and lamellar liquid crystalline (Lalpha) phases formed for n(c) = 6 and 7. The only liquid crystalline phase found in the OPOS system was a Lalpha phase. The NaOS H(I) phase was the only liquid crystalline phase that showed a linear relation between the 2H2O NMR quadrupolar splitting (deltaW) and Xsurf/X(W), where Xsurf and X(W) are the mole fractions of surfactant and water. The OPOS lamellae were found to be much thinner than expected, indicating a defect lamellar structure. This was further supported by the behavior of the quadrupolar splitting ofdeuterated OPOS. The anomalous behaviors of the 2H2O NMR quadrupolar splitting observed in the Lalpha phases of 1-heptylpyridinium octane-1-sulfonate and OPOS were interpreted in terms of changes in the population of the water molecules residing in different sites combined with a continuous rearrangement of the lamellae surface with the possible development of holes. The appearances of the phase diagrams were discussed in terms of surfactant molecular geometry and the packing of the amphiphiles in the aggregates formed.     

X-ray diffraction studies on mesophases of cetyl- and dodecyltrimethylammoniumbromide in liquid ammonia

We have studied solutions of the surfactants cetyltrimethylammoniumbromide (CTAB) and dodecyltrimethylammoniumbromide (DTAB) in liquid ammonia with respect to the formation of lyotropic phases. For this purpose, a set-up for performing X-ray scattering experiments at temperatures up to 120 degrees C on samples containing liquid ammonia has been developed. Both systems form hexagonal and monoclinic lyotropic phases above the dissolving temperature of the surfactant, thus representing the first examples for lyotropic phases in liquid ammonia, and for monoclinic phases in nonaqueous solvents. The phase diagrams of CTAB/liquid NH(3) and DTAB/liquid NH(3) show similarities to their respective aqueous systems. However, the regions of existence of monoclinic phases are much larger in the ammonia system, while the cubic phases, as observed in the water based systems, do not seem to exist. The liquid-crystalline phases found provide potentiality for preparing mesoporous, nitride-based solids.     

Polarization transfer solid-state NMR for studying surfactant phase behavior

The phase behavior of amphiphiles, e.g., lipids and surfactants, at low water content is of great interest for many technical and pharmaceutical applications. When put in contact with air having a moderate relative humidity, amphiphiles often exhibit coexistence between solid and liquid crystalline phases, making their complete characterization difficult. This study describes a (13)C solid-state NMR technique for the investigation of amphiphile phase behavior in the water-poor regime. While the (13)C chemical shift is an indicator of molecular conformation, the (13)C signal intensities obtained with the CP and INEPT polarization transfer schemes yield information on molecular dynamics. A theoretical analysis incorporating the effect of molecular segment reorientation, with the correlation time τ(c) and order parameter S, shows that INEPT is most efficient for mobile segments with τ(c) < 0.01 μs and S < 0.05, while CP yields maximal signal for rigid segments with τ(c) > 10 μs and/or S > 0.5 under typical solid-state NMR experimental conditions. For liquid crystalline phases, where τ(c) < 0.01 μs and 0 < S < 0.3, the observed CP and INEPT intensities serve as a gauge of S. The combination of information on molecular conformation and dynamics permits facile phase diagram determination for systems with solid crystalline, solid amorphous, anisotropic liquid crystalline, and isotropic liquid (crystalline) phases as demonstrated by experiments on a series of reference systems with known phase structure. Three solid phases (anhydrous crystal, dihydrate, gel), two anisotropic liquid crystalline phases (normal hexagonal, lamellar), and two isotropic liquid crystalline phases (micellar cubic, bicontinuous cubic) are identified in the temperature-composition phase diagram of the cetyltrimethylammonium succinate/water system. Replacing the succinate counterion with DNA prevents the formation of phases other than hexagonal and leads to a general increase of τ(c).     

PHASE EQUILIBRIA OF TETRAMETHYLDIOCTYL-DISILOXANE,WATER AND ORGANIC SOLVENTS

The phase diagrams for tetramethyldioctyldisiloxane (TDDS), water and several organic components were determined using refractive index, polarizing microscopy and low angle x-ray diffraction. The solubility limits of the alcohols were established by quantitative analysis and compared to the refractive index of known single phase mixtures. The non-ionic surfactants systems contained isotropic liquids of varying concentrations. Two lyotropic liquid crystal regions were discovered, one of lamellar structure and one consisting of a hexagonal array of closed packed cylinders. The character of the amphiphiles components to solubilize the TDDS is reflected in Ihe phase equilibria.     

Nonaqueous lyotropic liquid-crystalline phases formed by gemini surfactants in a protic ionic liquid

The aggregation behaviors of three Gemini surfactants [(C(s)H(2s)-α,ω-(Me(2)N(+)C(m)H(2m+1)Br(-))(2), s = 2, m = 10, 12, 14] in a protic ionic liquid, ethylammonium nitrate (EAN), have been investigated. The polarized optical microscopy and small-angle X-ray scattering (SAXS) measurements are used to explore the lyotropic liquid crystal (LLC) formation. Compared to the LLCs formed in aqueous environment, the normal hexagonal and lamellar phases disappear. However, with increasing the surfactant concentration, a new reverse hexagonal phase (H(II)) can be mapped over a large temperature range except for other ordered aggregates including the isotropic solution phase and a two-phase coexistence region. The structural parameters of the H(II) are calculated from the corresponding SAXS patterns, showing the influence of surfactant amount, alkyl chain length, and temperature. Meanwhile, the rheological profiles indicate a typical Maxwell behavior of the LLC phases formed in EAN.     

Investigation in monolayers of double-chain fluorocarbon amphiphiles Effect of headgroups on molecular packing and interaction between hydrocarbon and fluorocarbon monolayers

The surface pressure-area diagrams of double-chain fluorocarbon amphiphiles with different headgroup compositions show that the amphiphiles arrange almost perpendicularly to the water subphase and the structure of headgroups exerts significant influence on the amphiphile packing. Strong hydrogen bonding and weak electrostatic interaction favor the formation of stable monolayers. Perfluorooctanoic acid (FOA) cannot form monolayer at water/air interface and can only form liquid monolayer in subphase of calcium nitrate solution. Complete phase separation of palmitic acid and a fluorocarbon amphiphile with shorter hydrocarbon spacer group, 1, could be demonstrated in monolayers by using the phase rule of Crisp. The creation of phase-separated monolayers is possible when the monolayer is composed of a mixture of palmitic acid and a fluorocarbon amphiphile with longer hydrocarbon spacer group, 2. It can be suggested that the miscibility of hydrocarbon amphiphiles with fluorocarbon amphiphiles is determined by the hydrocarbon fraction of fluorocarbon amphiphiles.     

SYNERGETIC EFFECT OF SUCROSE AND ETHANOL ON FORMATION OF TRIGLYCERIDE MICROEMULSIONS

The phase behavior of soybean oil, a nonionic surfactant (ethoxylated monodiglycerides) and an aqueous phase of water containing ethanol, and sucrose was investigated at 35 and 40°C. A minimum concentration of 20 wt% ethanol was required for the formation of isotropic solutions. Addition of sucrose to the aqueous phase decreased the amount of ethanol required to form these solutions. The solubilization mechanism of the oil was investigated by small angle x-ray diffraction and polarized light microscopy. A stable lamellar liquid crystalline phase was formed for a mixture of 75/25 surfactant/sucrose solution (2.5 wt% sucrose). This phase was destabilized with increased concentrations of sucrose and liquid crystalline phases having hexagonal structures were favored at 8.75 wt% sucrose. At a ratio of 55/45 wt% of surfactant/sucrose solution (9 wt% sucrose) hexagonal structures were formed and could be destabilized or destroyed by addition of ethanol. The concept of stabilization and destabilization of liquid crystalline mesophases was applied to the solubilization of triglycerides in aqueous solutions. Two microemulsion regions were identified; oil-in-water (L₁) and water-in-oil (L₂) in systems containing soybean oil, ethoxylated monodiglycerides, and 20 wt% ethanol solution. At 55/45 wt% surfactant/20 wt% ethanol solution,7.5 wt% of soybean oil was solubilized. Addition of 10, 20, and 30 wt% sucrose, at the same ratio of surfactant to ethanol solution, increased the solubility of the oil to 9, 13.5, and 18 wt% respectively. In addition, the size of the L₁ phase increased and moved to the aqueous corner of the phase diagram and the size of the L₂ phase decreased.