P NMR investigation of a ringing gel phase and adjacent phases

The temperature-surfactant concentration phase diagram was examined for the dodecyltrimethylammonium dimethylphosphate/3-methyl-3-methoxybutanol/water ternary system. The phase diagram contained a highly elastic gel phase which is known as a “ringing gel phase”. The ringing gel phase and adjacent phases in the ternary system were investigated by polarized optical microscopy, freeze-fracture transmission electron microscopy, and ³¹P NMR. Globular textures were observed in an optically isotropic gel phase. Since the globules were larger than those found in an isotropic solution, the texture consists of domains of aggregated units in the cubic (I₁) phase. Structure units of domains are equivalent to microemulsions which are constructed by surfactant molecules and swollen by alcohol in the isotropic (L₁) phase. Characteristic polarized microscopic textures were visualized in two phases with higher surfactant concentrations. These phases were identified as being hexagonal (H₁) and lamellar (L) liquid crystals which was confirmed by transmission electron microscopy. The ³¹P NMR signal of the ringing gel showed a sharp singlet the same as that of the L₁ phase, indicating the fully averaged anisotropic interaction of the aggregates. The characteristic NMR signals of the anisotropic hexagonal and lamellar liquid crystal phases displayed chemical shielding with an asymmetric lineshape.     

Electrical conductivity of lyotropic phases of dodecylbenzenesulphonates with Li+, Na+, and K+ ions in water

The electrical conductivity of dodecylbenzenesulphonate (DoBS) ionic lyotropic liquid crystal of the systems: LiDoBS (dodecylbenzenesulphonic acid lithium salt)/water, NaDoBS (dodecylbenzenesulphonic acid sodium salt)/water, and KDoBS (dodecylbenzenesulphonic acid potassium salt)/water were investigated by impedance spectroscopy in the frequency range from 0.5 Hz to 0.5 MHz. The electrical conductivity of lyotropic LiDoBS was higher than that of isotropic phase. The electrical conductivity isotropic KDoBS and NaDoBS was higher than the conductivity of lyotropic ones. The temperature dependence of electrical conductivity was investigated in the systems LiDoBS/water and KDoBS/water for different phases. The activation energy of electrical conductivity is lowest for the normal hexagonal phase LiDoBS/water. Such systems based on anionic surfactants are of interest as the electrolyte for the supercapacitors.     

Phase Behavior of Commercial AES/Ethanol/H2O Ternary System

Phase behavior containing alkyl ethoxysulfates (AES), ethanol, and H₂O over the whole concentration range was explored at 25°C. The system exhibited an isotropic solution phase (L), two different liquid crystalline phases: hexagonal phase (H), lamellar phase (Lα), and a biphasic region appearing with the ethanol concentration increasing. Polarized optical microscopy and small angle x-ray scattering were applied to characterize liquid crystalline phases. Direct two-phase titration and liquid chromatography–mass spectrometry (LC–MS) were employed to analyze the AES activity and homologues composition of the particles appearing in two-phase region.     

Monoolein cubic phases containing hydrogen peroxide

Monoolein (MO) cubic phases were prepared by hydrating MO using distilled water or 12 wt.% H₂O₂ solution so that the content of aqueous phase in the cubic phase is 30 wt.%. The thermal transition of the isotropic cubic phase to reversed hexagonal phase was observed on a polarizing photomicroscope and the transition temperature was found to be around 65 °C on a differential scanning calorimeter (DSC). Small-angle X-ray scattering (SAXS) patterns indicated the cubic phases had diamond surfaces. The cubic phase released H₂O₂ into an aqueous phase in a saturation manner so that approx. 50% of total loaded H₂O₂ release in the first 10 h and thereafter relatively slow was observed over 40 h. The cubic phase was stable at 45 °C for 56 days before it broke down into an oily phase and an aqueous phase in 70 days. According to ¹H NMR spectrum, glycerol moiety and ---CH₂=CH₂--- of the oily phase were detected less in number than those of intact MO. Therefore, the hydrolysis and the oxidation of MO would be responsible for the breakdown of the cubic phase. The tensile adhesive forces of the cubic phases were higher than a skin-adhesive patch prepared using polyacrylate. The cubic phase containing H₂O₂ could be used as a topical disinfected gel for a wounded skin.     

Electron microscopic and light scattering observation on a system with two iridescent phases

Electron microscopic observations and classical light-scattering measurements have been carried out for dodecyldimethylaminoxide/hexanol/water mixtures in the concentration range where iridescent colors occur. This system has two different iridescent phases. The iridescent phase with more hexanol forms quickly, and the phase with less hexanol forms very slowly. Three different isotropic phases which show strong flow birefringence are found near both iridescent phases. The electron microscopic pictures show clearly that only one of these isotropic phases with strong flow birefringence is a bicontinuous sponge phase (L_3h -phase). This is the phase which comes out by adding some alkanol to the upper lamellar phase. The flow birefringent phase below the lower lamellar phase forms unilamellar vesicles. The flow birefringent phase which occurs between both iridescent phases contains multilamellar vesicles and is shown to be a precursor of a lamellar phase.     

From smectic to columnar phase of polypedal liquid crystals based on tetrathiafulvalene/1,3-dithiol-2-thione and cholesterol

Bipedal 1,3-dithiole-2-thiones attached two cholesteryl through a ω-thioalkanoyloxy spacer of varying length were synthesized. The bipedals were easily transformed to the appropriate tetrapedal tetrathiafulvalene derivatives by self-coupling reaction in net triethyl phosphite. All the synthesized compounds exhibit mesogenic phases in a wide temperature region, no crystallization but vitrifying to form glassy mesogens during cooling from the isotropic melt. The liquid crystals with shorter spacer (n=2-6) exhibited only a smectic A phase and those with the longest spacer (n=7) exhibited only a hexagonal columnar. In these series, the molecular packing depended on the length of spacers.     

Low-frequency dielectric relaxation in columnar hexagonal and micellar inverse cubic mesophases

Dielectric measurements on four diols showing columnar hexagonal and micellar cubic phases were carried out. Besides the known fast local reorientation in theGHz-range, a new absorption in theMHz region was detected. This mechanism was interpreted as a collective motion of the molecules inside the micelles or cylindrical aggregates. The absorption was also found in the isotropic phase. Based upon the interpretation given, the molecular aggregates should also exist in the isotropic state. The electrical conductivity strongly supports the classification as inverse phases.     

Nanoorganization and Phase Behavior of Mixtures of Nicotinic Acid with Dodecylbenzenesulfonic Acid

Abstract

Mesomorphically ordered structures and phase behavior of the mixtures of nicotinic acid (NICA) and dodecylbenzenesulfonic acid (DBSA) were investigated by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and polarized optical microscopy (POM). The POM observations revealed that the NICA–DBSA mixtures spontaneously formed liquid crystalline phases, although both NICA and DBSA were not liquid crystalline molecules. The NICA–DBSA mixtures formed ordered lamellar structures in DBSA‐rich mixtures and hexagonal cylinder structure in NICA‐rich mixtures. The mesomorphically ordered structures and optical anisotropy were caused by hierarchical interactions in the NICA–DBSA mixtures. The phase diagram divided into five regions—optically isotropic disordered phase, optically isotropic lamellar phase, optically anisotropic lamellar phase, optically anisotropic cylinder phase, and crystalline solid phase—is drawn by summarizing the XRD and POM results.     

碲化镓纳米片中单斜晶相和六方晶相共存的光谱特征（英文）

快速发展的二维层状材料为构建新型高效的微纳发光器件和光电探测器件提供了新的平台.其中碲化镓纳米片备受关注,这是因为碲化镓从少层到块体都具有极强的发光性能,因而可以降低二维微纳器件的制备条件.然而碲化镓纳米片具有单斜和六方等多种晶相,使其发光特性和光谱结构异常复杂,目前还缺少对不同厚度碲化镓纳米片荧光光谱的系统研究.本文研究了不同厚度碲化镓纳米片的荧光光谱和拉曼光谱,以及荧光光谱从低温(4 K)到室温的演化行为.通过光谱分析,发现单斜晶相和六方晶相可能同时共存于多层碲化镓纳米片中.为了阐述相关实验结果,构建了如下原子结构模型:其中六方晶相位于纳米片的顶层与底层,而单斜晶相位于纳米片的中间位置.基于温度依赖的荧光光谱,可以获得六方晶相的光学带隙为1.849 eV,且该激子峰只能在较高温度(>200 K)下和声子辅助下才能表现出显著的荧光发射行为.进一步的实验结果确定了六方晶相的激子-声子相互作用强度约为1.24 meV/K.本工作证实了碲化镓纳米片中单斜晶相与六方晶相共存的实验现象,为研究碲化镓纳米片的晶相变化和激子动力学,以及探究碲化镓的奇异物理化学特性,提供了新的见解.     

Phase formation in sodium dodecylsulfate solutions in the presence of salicylic acid for preconcentration purposes

The occurrence of surfactant-rich phases in aqueous sodium dodecylsulfate solutions in the presence of salicylic acid was investigated. The effect of acidity, electrolyte and salicylic acid concentrations on the parameters of phase formation were studied. Optimal conditions for microcomponent preconcentration were found. The features of solubilization efficiency changes of organic substances depending on their charge and hydrophobicity were established. High efficacy of preconcentration of strongly hydrophobic, positively charged substrates by low-temperature surfactant-rich phases obtained in the sodium dodecylsulfate-salicylic acid-sodium chloride ternary system is shown.     

Characterization of lecithin-based microemulsions used as media for a cholesterol oxidase-catalyzed reaction

Microemulsions stabilized by soybean lecithin and ethanol have been characterized with respect to phase behavior, distribution of the ethanol cosolvent, conductivities, viscosities, and volume fractions of the different phases in Winsor III systems. The conductivities and viscosities of the surfactant-rich phase in the Winsor III system indicate that this phase exhibits a bicontinuous structure. The reaction yield at 298.2K for the enzymatic conversion of cholesterol to cholestenone by cholesterol oxidase performed in a Winsor III system containing water, lecithin, hexadecane, and ethanol is low.     

Aggregation-driven,re-entrant isotropic phase in a smectic liquid crystal material

An azobenzene-core chiral mesogen designed for a photoactive ferroelectric liquid crystal system with switchable polarisation displays a highly unusual phase sequence, with a re-entrant, optically isotropic, fluid phase found below smectic phases in mixtures with high enantiomeric purity. The re-entrant isotropic phase is found on the basis of X-ray scattering and freeze-fracture transmission electron microscopy experiments not to be a cubic or other highly ordered phase but instead a translationally disordered liquid. The material also forms a gel under a wide range of concentrations in 50:50 ethanol/chloroform solutions. Ultraviolet/visible and infrared spectroscopy and quantum chemistry calculations suggest that the primary unit in the re-entrant isotropic and gel phases is a dimer composed of molecules crossed by about 90°, which hinders the formation of crystal phases and forms tubules of helical aggregates in the gel phase.     

Ordering in surfactant mixtures induced by polymers

We studied ternary mixtures of nonionic surfactant (C12E6, n-dodecyl hexaoxyethylene glycol monoether), polymer (PEG, polyethylene glycol), and water. A small amount of PEG induces demixing into the polymer-rich and surfactant-rich phases in the ternary PEG/C12E6/water mixture. Above a certain concentration and/or molecular weight of PEG, the surfactant-rich phase orders, even in a solution consisting of a few percent of surfactant. The phase boundary acts as a semipermeable membrane, and the equilibrium is determined by the chemical potential of water in two phases. The explicit expression for the amount of PEG needed to order C12E6 water solution is given and verified experimentally. The analysis of the coexistence conditions leads to the conjecture that only two oxygen atoms in the outward part of the hydrophilic surfactant head strongly affect the chemical potential of water. Our methodology is generic, i.e., on the same basis one can design a similar experiment for any surfactant/polymer/water system and find the right proportions of polymer that induce order in a surfactant-rich phase.     

Lyotropic liquid crystalline phases in a ternary system of 1-hexadecyl-3-methylimidazolium chloride/1-decanol/water

Lyotropic liquid crystals formed in a ternary system of 1-hexadecyl-3-methylimidazolium chloride ([C16mim]Cl), 1-decanol, and water at 25 degrees C are reported. The hexagonal and lamellar phases were characterized by small angle X-ray scattering and polarizing optical microscopy. In the phase diagram, the system shows two isotropic liquid phases, a hexagonal phase connected to the [C16mim]Cl-water axis, and a lamellar phase in the center. The formation of liquid crystalline phases is believed to arise from a hydrogen-bonded network comprised of an imidazolium ring, anion, 1-decanol, and water. In the liquid crystal, the intercalation of 1-decanol between neighboring [C16mim]Cl molecules favors the appearance of lamellar phases. The phase behavior of the present system is discussed in comparison with a similar ternary system of cetyltrimethylammonium bromide (CTAB).     

Phase transition in non-ionic surfactant—water systems as studied by Raman spectrometry: Part I. Water—α-octyl-ω-hydroxypentakis (oxyethylene)

The Raman spectra of α-octyl-ω- hydroxypentakis (oxyethylene) (C₈E₅) in water—(C₈E₅) systems have been studied for various compositions and at various temperatures. Continuous changes of the spectra are observed in the isotropic phase, when varying the composition, which is maximum when approaching the hexagonal phase boundary. The transition between the isotropic and hexagonal phases brings about an important change in the ν(CH) region. A tentative interpretation of these results is given.     

Phase separation in non-ionic surfactant Triton X-100 solutions in the presence of phenol

The influence of concentration conditions and acidity on the phase separation in non-ionic surfactants Triton X-100 solutions in the presence of phenol was investigated. It was shown that the addition of small amounts of phenol results in the decrease of the cloud point temperature of Triton X-100 solutions. On the other hand, the addition of phenol into the investigated system resulted in the decrease of the hydration values of surfactant-rich phases and the increase of their hydrophobicity. The extraction degree and distribution coefficient of phenol between the water and the surfactant-rich phases were studied. On the basis of data obtained the molar parts of water, phenol and Triton X-100 in the non-ionic surfactant-rich phases formed at different concentration conditions were calculated. Possibilities of the application of phenol-induced micellar extraction for microcomponents preconcentration were estimated.     

Phase behavior of a thermotropic cubic mesogen 4'-n-hexadecyloxy-3'-nitro- biphenyl-4-carboxylic acid under pressure

The phase behavior of an optically isotropic cubic mesogen 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-16) was investigated under hydrostatic pressures up to 200 MPa using a high-pressure DTA, a polarizing optical microscope equipped with a high-pressure hot-stage and a wide-angle X-ray diffractometer equipped with a high-pressure vessel. In the T vs. P phase diagram constructed in the heating mode, a triple point exists at 54±1 MPa and 205±1°C for the SmC, cubic, and SmA phases. A new mesophase, denoted here as X, appears in place of the cubic phase under pressures above about 60 MPa, while the X phase appears on cooling in the whole pressure region studied. Thus the X phase is a monotropic (metastable) phase between the SmA and Cub phases in the low pressure region, while being an enantiotropic phase between the SmA and SmC phases in the high pressure range. The X phase exhibits broken-fan or sand-like textures under pressure and a spot-like diffraction pattern, indicating the birefringent feature and no layered structure. It is suggested that the X phase is tetragonal or hexagonal columnar phase. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermotropic liquid crystals of 1H-imidazole amphiphiles showing hexagonal columnar and micellar cubic phases

The linear and polycatenar type 1H-imidazole amphiphiles showing a strong self-assembly tendency to build various supramolecular structures in bulk were synthesized by the esterification reaction of 4′-alkyloxy phenols (for 1-4) and hydroxyphenyl trialkyloxybenzoates (for 5-7) with 4-chlorocarbonyl imidazole. The linear 1H-imidazole amphiphiles formed thermotropic smectic phases, but compound 4 with an ethyl group instead of hydrogen on 1N did not show a mesophase. The polycatenar type 1H-imidazole amphiphiles (5-7) formed thermotropic hexagonal columnar and cubic phases. A phase transition was observed from a columnar phase to a cubic phase as the temperature increased on heating, and vice versa on cooling. In the POM study for compounds 5-7, optically isotropic phases first appeared on cooling from the isotropic melts, and then birefringent mesophases with a nonspecific texture appeared on further cooling. The X-ray analysis shows that the optically isotropic phases were very likely micellar cubic phases with Pm3n symmetry. The birefringent phases were confirmed as hexagonal columnar phases.     

Induced smectic phases in phase diagrams of binary nematic liquid crystal mixtures

To elucidate induced smectic A and smectic B phases in binary nematic liquid crystal mixtures, a generalized thermodynamic model has been developed in the framework of a combined Flory-Huggins free energy for isotropic mixing, Maier-Saupe free energy for orientational ordering, McMillan free energy for smectic ordering, Chandrasekhar-Clark free energy for hexagonal ordering, and phase field free energy for crystal solidification. Although nematic constituents have no smectic phase, the complexation between these constituent liquid crystal molecules in their mixture resulted in a more stable ordered phase such as smectic A or B phases. Various phase transitions of crystal-smectic, smectic-nematic, and nematic-isotropic phases have been determined by minimizing the above combined free energies with respect to each order parameter of these mesophases. By changing the strengths of anisotropic interaction and hexagonal interaction parameters, the present model captures the induced smectic A or smectic B phases of the binary nematic mixtures. Of particular importance is the fact that the calculated phase diagrams show remarkable agreement with the experimental phase diagrams of binary nematic liquid crystal mixtures involving induced smectic A or induced smectic B phase.     

New compounds with a TGBA-TGBC-SmC* phase sequence

A new series of lactic acid derivatives has been prepared with molecular cores consisting of two laterally substituted biphenyls connected by an ester group. The compounds exhibited the TGBA phase in a broad temperature range. In addition, for some compounds, a narrow blue phase was found above the TGBA phase on cooling from the isotropic phase. Except for the compound with the shortest chain, the TGBC phase appeared below the TGBA phase. The low temperature SmC* phase existed within the interval up to 80 K, including the overcooled state, which was down to room temperature. In the compounds studied a strong pre-transitional phenomenon took place manifested as a broad peak on the differential scanning calorimetry plot in the isotropic phase. The phases were established on the basis of a planar sample and free-standing film microscope observation. Small angle X-ray diffraction measurements provided information about layer spacing, d, and confirmed the phase assignment. Dielectric spectroscopy revealed the soft and Goldstone modes in the respective TGBA and SmC* phases.