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1.
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.  相似文献   

2.
The esterification of hexanoic acid and 1-pentanol catalyzed by the lipase fromChromobacterium viscosum was studied at 298.2 K using different Winsor systems as reaction medium. The microemulsion systems consisted of brine and alkane stabilized by the anionic surfactant sodium dodecylsulphate and a short-chained alcohol. The alcohol acts both as a reactant and as a part of the reaction medium. Therefore, it is of great fundamental interest to know the phase behavior of the used microemulsion systems. Partial phase diagrams were determined and the efficiency of different alcohols on the transition from a Winsor I system to a Winsor III or a Winsor IV system with bicontinuous structure and further to a Winsor II system was investigated. The investigated alcohols were 2-methyl-1-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, and 1-hexanol. The aqueous medium consisted of 0.5 m NaCl(aq) or a phosphate buffer (pH=7) and the organic medium of octane or 2,2,4-trimethyl pentane. A long alkyl chain of the alcohol or a branching far from the hydroxyl group gives a more efficient cosurfactant and a transition from Winsor I to Winsor III or Winsor IV at lower alcohol contents. In the Winsor III system the yield of 1-pentyl hexanoate is twice as high as the yield in the bicontinuous Winsor IV system.  相似文献   

3.
The present article describes an equilibrium theory for determining binary phase diagrams of various crystalline-amorphous polymer blends by taking into account the contributions from both liquid-liquid phase separation between the constituents and solid-liquid phase transition of the crystalline component. An analytical expression for determining a crystal-amorphous interaction parameter is deduced based on the solid-liquid transition, involving the solidus and liquidus lines in conjunction with the coexistence curve of an upper critical solution temperature type. Of particular importance is that the crystalline-amorphous interaction parameter can be determined directly from the melting point depression data. The present analysis is therefore different from the conventional Flory-Huggins interaction parameter, which is associated with the liquid-liquid phase separation. The validity of the present theory is tested with the experimental phase diagrams of blends of poly(ethylene oxide)/diacrylate and poly(vinyl alcohol)/cellulose.  相似文献   

4.
扩散致相转化法制备结晶性聚合物多孔膜   总被引:6,自引:0,他引:6  
介绍了扩散致相转化法制备结晶性聚合物多孔膜的研究现状。其三元等温成膜体系的相图包含液-液分相和固-液分相两种相分离方式,是理解成膜过程的重要工具,总结了成膜机理和膜的结构形貌:单纯S-L相分离生成粒子状对称膜结构;单纯L-L相分离生成蜂窝状非对称膜结构;两种相分离方式竞争发生将生成多样的混合膜结构。铸膜液浓度、非溶剂种类、铸膜溶剂组成、凝胶浴组成、制膜温度是影响膜结构形貌的主要因素。  相似文献   

5.
We investigate the critical lines of polymer mixtures in the presence of their vapor phase at the mathematical double point, where two critical lines meet and exchange branches, and its environment. The model used combines the lattice gas model of Schouten, ten Seldam and Trappeniers with the Flory-Huggins theory. The critical line structure is displayed for various combinations of the chain length and system parameters in the pressure (P)-temperature (T) plane, as is usually done with experimental results. This type of work sheds light on the essential transition mechanism involved in the phase diagram's change of character, such as multi-critical points and mathematical double points, which are of great practical importance in supercritical fluid extraction processes. The P, T diagrams are discussed in accordance with the Scott and van Konynenburg binary phase diagram classification. We found that our P, T plots were in agreement with type II, type III, or type IV phase diagram behaviors. We also found that some of our phase diagrams represent the liquid-liquid equilibria in polymer solutions and mixtures.  相似文献   

6.
The phase diagram at 298.2 and 281.2 K for the ternary system water-butylammonium decanoate-decane has been determined. An isotropic solution phase extending from the water corner to the decane corner was obtained without any macroscopic phase separation. A large two-phase region extending from the water-decane axis was also observed. In addition to these phases, an anisotropic and optically birefrigent liquid crystalline phase is formed below 290.3 K. Sound velocity, conductivity, and viscosity measurements were used successfully for studies of microstructural transitions in the isotropic solution phase. From these measurements, it was concluded that a transition from normal micelles to reverse micelles takes place while passing through a bicontinuous region.  相似文献   

7.
We study the morphology of spinodal decompositions (SDs) in mixtures of a liquid crystal and a colloidal particle by solving time-dependent Landau-Ginzburg equations for a conserved order parameter (concentration) and two nonconserved order parameters (orientation and crystallization). We numerically examine the coupling between concentration, nematic ordering, and crystalline ordering in two dimensional fluid mixtures, coexisting a nematic and a crystalline phase. On increasing the concentration of colloidal particles, we have three different SDs: a nematic order-induced SD, a phase-separation-induced SD (PSD), and a crystalline-order-induced SD (CSD). In NSD, the phase ordering can lead to fibrillar and cellular networks of the minority colloidal-particle-rich phase in early stages. In the PSD, we find a bicontinuous network structure consisting of a nematic phase rich in liquid crystal and a crystalline phase rich in colloidal particles. In the CSD, nematic droplets can be formed in a crystalline matrix. Asymmetric mixtures of a liquid crystal and a colloidal particle lead to rich varieties of morphologies.  相似文献   

8.
热致相分离法制聚偏氟乙烯微孔膜稀释剂的选择   总被引:3,自引:0,他引:3  
依据聚偏氟乙烯(PVDF)、邻苯二甲酸二甲酯、水杨酸甲酯、卡必醇醋酸酯、三醋酸甘油酯、邻苯二甲酸二正丁酯(DBP)、苯乙酮和二苯甲酮(DPK)的Hansen溶度参数及其相对介电常数, 选择能与PVDF以液-液相分离机理进行热致分相的稀释剂, 制备了具有双连续结构的微孔膜. 通过比较PVDF-稀释剂间的溶度参数及相对介电常数的差异, 发现PVDF-DBP体系和PVDF-DPK体系有发生热致液-液相分离的可能. 实时观察上述两个体系的分相过程并测定其结晶温度, 当PVDF质量分数低于30%时, 随着温度的降低, PVDF-DPK体系发生液-液相分离. 根据PVDF-DPK体系相图, 通过控制PVDF含量和降温条件, 无须添加非溶剂或拉伸工艺, 就可以制备出具有双连续结构的PVDF微孔膜.  相似文献   

9.
Supramolecular structures and morphologies of nonsintered, sintered, and radiation-modified suspension-polymerized PTFEs are investigated via scanning electron microscopy. Gamma irradiation is performed below and above the melting point of the crystalline phase. The fibrillar supramolecular structure of the nonsintered PTFE is preserved after its sintering. However, some regions of fibrils in the sintered PTFE form lamellas elongated perpendicularly to the orientation of fibrils. Irradiation of PTFE below the melting temperature at 20 and 200°C is not accompanied by a qualitative change in its morphology. Irradiation above the melting temperature results in reorganization of the PTFE structure, namely, formation of spherulites consisting of radially oriented fibrils.  相似文献   

10.
Nanopowder of yttrium aluminum garnet (YAG, Y3Al5O12) doped with neodymium ions (Nd:YAG) was prepared in the water/cetyltrimethylammonium bromide/1-butanol/n-heptane system. Aluminum, yttrium, and neodymium nitrates were used as starting materials, and ammonia was used as a precipitating agent. Coprecipitate hydroxide precursors where thermally treated at 900 degrees C to achieve the garnet phase. The starting system with and without reactants was characterized by means of the small-angle neutron scattering technique. The system, without reactants, is constituted by a bicontinuous structure laying near the borderline with the lamellar phase region. The introduction of nitrates stabilizes the bicontinuous structure, while the presence of ammonia induces a transformation from the bicontinuous phase to a lamellar phase. Nd:YAG nanopowder was characterized by wide-angle X-ray scattering, transmission electron microscopy, gas adsorption, and photoluminescence spectroscopy. By comparison with a sample prepared by the conventional coprecipitation method, the obtained Nd:YAG nanopowder is constituted by smaller crystalline nanoparticles showing a lower tendency to agglomerate. In addition, the nanoparticles present a well-defined spherical shape. Photoluminescence spectroscopy confirms that the doping Nd3+ ions substitute Y3+ ions in the YAG crystalline lattice. The Nd3+ lifetime value, obtained from the luminescence decay curves, was 286 +/- 10 micros, higher than the single-crystal value (255 micros) and much higher than the nanopowder value obtained by the conventional coprecipitation method (75 micros).  相似文献   

11.
With a view to discovering a new family of lipids that form inverted cubic phases, the aqueous phase behavior of a series of lipids with isoprenoid-type hydrophobic chains has been examined over a temperature range from -40 to 65 degrees C by using optical microscopy, DSC (differential scanning calorimetry), and SAXS (small-angle X-ray scattering) techniques. The lipids examined are those with 5,9,13,17-tetramethyloctadecyl and 5,9,13,17-tetramethyloctadecanoyl chains linked to a series of headgroups, that is, erythritol, pentaerythritol, xylose, and glucose. All of the lipid/water systems displayed a "water + liquid crystalline phase" two-phase coexistence state when sufficiently diluted. The aqueous phase structures of the most diluted liquid crystalline phases in equilibrium with excess water depend both on the lipid molecular structure and on the temperature. Given an isoprenoid chain, the preferred phase consistently follows a phase sequence of an H II (an inverted hexagonal phase) to a Q II (an inverted bicontinuous cubic phase) to an L alpha (a lamellar phase) as A* (cross-section area of the headgroup) increases. For a given lipid/water system, the phase sequence observed as the temperature increases is L alpha to Q II to H II. The present study allowed us to find four cubic phase-forming lipid species, PEOC 18+4 [mono- O-(5,9,13,17-tetramethyloctadecyl)pentaerythritol], beta-XylOC 18+4 [1- O-(5,9,13,17-tetramethyloctadecyl)-beta- d-xylopyranoside], EROCOC 17+4 [1- O-(5,9,13,17-tetramethyloctadecanoyl)erythritol], and PEOCOC 17+4 [mono- O-(5,9,13,17-tetramethyloctadecanoyl)pentaerythritol]. The values of T K (hydrated solid-liquid crystalline phase transition temperature) of the cubic phase-forming lipids are all below 0 degrees C. Quantitative analyses of the lipid molecular structure-aqueous phase structure relationship in terms of the experimentally evaluated "surfactant parameter" allow us to rationally select an optimum combination of hydrophilic/hydrophobic part of a lipid molecule that will form a desired phase in a desired temperature range.  相似文献   

12.
We report for the first time on the templating effect of β-lactoglobulin amyloid-like fibrils to synthesize gold single crystals of several decades of μm in dimensions. The gold single crystals were produced by reducing an aqueous solution of chloroauric acid by β-lactoglobulin amyloid protein fibrils. Atomic force microscopy, conventional and scanning transmission electron microscopy, electron diffraction and optical microscopy techniques were combined to characterize the structure of the gold crystals. The single-crystalline features of these macroscopic gold crystals are witnessed by their distinctive hexagonal and triangular shape and are confirmed by selected area electron diffraction (SAED). UV-vis absorption spectrum, recorded after a reaction time of 6h at the heating temperature of 55°C showed a surface plasmon resonance peak at 540 nm. With the increase of reaction time to 24h, the absorption spectrum peaks shift to a very broad and higher wavelength region extending up to near infrared region. Remarkably, these single crystalline gold crystals show auto fluorescence when illuminated to UV lamp. Further increase in β-lactoglobulin amyloid fibrils concentration above the isotropic-nematic transition, drives the formation of gold single crystals microplates stacking together and self-assembling into new hierarchical, layered protein-gold hybrid composites.  相似文献   

13.
Celecoxib (clxb) is an important drug for treatment of rheumatoid arthritis and osteoarthritis by specifically inhibiting the enzyme cyclooxygenase-2 (COX-2). Clxb is a type 2 drug characterized by low water solubility (<5 mug/ml) and fast transmembrane transport. The present formulations require high dosage since the transmembrane transport fluctuates and is very difficult to control. Dissolving the drug within an oil phase was not practical since its dissolution was very small and its dispersion in water was impossible. In our recent studies, we learned to construct U-type phase diagrams and to formulate reverse microemulsions (oil-based concentrates) that are progressively and fully dilutable with aqueous phase. In the present study, we solubilized clxb in nanostructures of reverse micelles of U-type nonionic microemulsions that consisted of R(+)-limonene, alcohol, propylene glycol (PG), and hydrophilic surfactant (Tween 60). The solubilization capacity of the drug in these systems is many times higher than in either the oil or the aqueous phase. The clxb solubilized microemulsions are fully diluted with aqueous phase without phase separation. The solubilization capacity decreases as the water content increases. Electrical conductivity, viscosity, and self-diffusion (SD) coefficients of the microemulsion components were measured along a suitable water dilution line. The three major microemulsion regions were detected and the transitions between the W/O to bicontinuous phase and from this phase to the O/W droplets were identified (at 30 and 70 wt% aqueous phase, respectively). From the SD coefficients, it was found that the drug is initially solubilized at the interface of the W/O droplets and there are no significant structural changes. The transition to a bicontinuous phase occurs at the same water content as in the empty (i.e., without drug) system. From the viscosity profiles, we concluded that the drug affects the structure of the bicontinuous phase as reflected in the water content at which the oil-continuous network is destroyed and full inversion occurs (50 vs 55 wt% in the drug-loaded system). Upon further dilution the drug remains solubilized at the interface and is oriented with its hydrophilic part facing the water, and is strongly affects the inversion to O/W droplets. From Small Angle X-ray Scattering (SAXS) measurements we learned that the drug effects the structure of microemulsion droplets and forms "ill-defined structures," probably less spherical. Yet, the overall droplet sizes at the high dilutions did not change very much.  相似文献   

14.
Spherulite morphology and growth kinetics of poly(octamethylene terephthalate) (POT), cast on single-side glass or confined between two slides in thin-film forms, were characterized using polarized versus nonpolarized optical microscopy, scanning electron microscopy (SEM), and wide-angle X-ray (WAXD) analysis. POT can simultaneously display solely one type of spherulite or dual types of spherulites (double-ring-banded and ringless ones), depending on T c or T max imposed. Fractions of these two types depend on T c when quenched from a fixed T max = 160 degrees C. At lower T c's, POT exhibits higher crystallization rates leading to higher fractions of ringless spherulites; at higher T c's, POT exhibits lower crystallization rates leading to ring-banded spherulites. At intermediate to high T c's where the growth kinetics of POT could be monitored, the ring-band type dominates and the fraction of ringless spherulites is insignificantly small. Both ringless and ring-banded spherulites can be seen in regime III ( T c = 70-110 degrees C), with fractions of ringless type of spherulites decreasing with temperature. Thus, growth kinetics for POT was mainly focused on the regime of ring-banded spherulites. In regime III, the ring-band pattern is more orderly concentric with smaller inter-ring spacing (1-2 mum) for lower T c's but intermediately larger spacing (3-5 mum) for higher T c's. The orderly lamellar orientation in the ring-bands in contrast with the inter-ring valley region is discussed. In regime II (115 degrees C and above), the ring-band pattern is first distorted to highly zigzag irregularity at higher T c's and then eventually disappears at extremely high T c, with the lamellar crystals eventually turning dendritic with no rings. Apparently, the types of spherulites in polymers are more influenced by the growth rates as determined by T c and slightly less by T max, but not by the substrate surface nucleation.  相似文献   

15.
Hybrid dendrimers, obtained by complete monofunctionalization of the peripheral amines of a "zero-generation" polyethyleneimine dendrimer, provide structurally diverse lamellar, columnar, and cubic self-organized lattices that are less readily available from other modified dendritic structures. The reaction of tris(2-aminoethyl)amine (TREN) with 4-dodecyloxybenzimidazolide provides only the corresponding zero-generation TREN dendrimer. From the mixture of tri- and disubstituted TREN derivatives obtained from first-generation self-assembling dendritic imidazolides, the hybrid dendrimer and a twin dendron could be separated, purified, and characterized. The hybrid dendrimers display smectic, columnar hexagonal (Phi(h)), and cubic (Pm_3n) lattices. The TREN twin dendrons, on which only two peripheral amines have been acylated, exhibit centered-rectangular columnar (Phi(r-c)), Phi(h), and Pm_3n lattices. The existence of a thermoreversible Phi(h)-to-Pm_3n phase transition in the first-generation hybrid dendrimers and twin dendrons is exploited to elucidate an epitaxial relationship between the two mesophases. We postulate a mechanism by which the transition proceeds. The thermoreversible Phi(h)-to-Pm_3n phase change is accompanied by optical property changes that are suitable for rudimentary signaling or logic functions. This structural diversity reflects the quasiequivalence of flat-taper and conical self-assembling dendrons and the ability of flexible dendrimers to accommodate concomitant conformational and shape changes.  相似文献   

16.
Some mixtures of two cationic lipids including phospholipid compounds (O-ethylphosphatidylcholines) as well as common, commercially available cationic lipids, such as dimethylammonium bromides and trimethylammonium propanes, deliver therapeutic DNA considerably more efficiently than do the separate molecules. In an effort to rationalize this widespread "mixture synergism", we examined the phase behavior of the cationic lipid mixtures and constructed their binary phase diagrams. Among a group of more than 50 formulations, the compositions with maximum delivery activity resided unambiguously in the solid-liquid crystalline two-phase region at physiological temperature. Thus, the transfection efficacy of formulations exhibiting solid-liquid crystalline phase coexistence is more than 5 times higher than that of formulations in the gel (solid) phase and over twice that of liquid crystalline formulations; phase coexistence occurring at physiological temperature thus appears to contribute significantly to mixture synergism. This relationship between delivery activity and physical property can be rationalized on the basis of the known consequences of lipid-phase transitions, namely, the accumulation of defects and increased disorder at solid-liquid crystalline phase boundaries. Packing defects at the borders of coexisting solid and liquid crystalline domains, as well as large local density fluctuations, could be responsible for the enhanced fusogenicity of mixtures. This study leads to the important conclusion that manipulating the composition of the lipid carriers so that their phase transition takes place at physiological temperature can enhance their delivery efficacy.  相似文献   

17.
The thermotropic behaviour of sodium oleate (NaOl) has been studied in the temperature range 10–125°C by using Fourier transform-Raman spectroscopy, X-ray diffraction and differential scanning calorimetry (DSC). The temperature dependence of conformationally sensitive bands in the CH2 stretching (2800–2900 cm−1), C–C stretching (1050–1150 cm−1) and CH3 rocking region (830–900 cm−1) has been used to characterize the order/disorder behaviour of alkyl chains. It is found that in phase I, NaOl exhibits the crystalline ordered lamellar structure with a repeat period of 4.51 nm. The first broad peak in the DSC trace is due to superposition of two transitions (phase I to phase II and phase II to phase III), therefore, it is not possible to determine the lamellar structure of phase II. This broad transition from phase I to phase III is associated with the melting of methyl-sided chains and increase in gauche conformers in carboxylate-sided chains. Finally, NaOl undergoes a transition from crystalline to a liquid crystalline phase IV, which is associated with the melting of the carboxylate-sided chain.  相似文献   

18.
Blend of poly(ε-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) containing 27.5 wt% of acrylonitrile was studied. The PCL/SAN blend having LCST (lower critical solution temperature) phase boundary above the melting point Tm of PCL offered an excellent opportunity to investigate the competition of liquid-solid phase transition (crystallization) and liquid-liquid phase transition (phase dissolution). A blend with the critical composition (80/20 PCL/SAN) underwent a temperature-jump above LCST to proceed spinodal decomposition, yielding a regularly phase-separated structure (SD structure). Then, it was quenched to the temperatures below Tm at which both the crystallization and the phase dissolution could occur. By transmission electron microscopy it was found that during isothermal annealing after quenching to high temperatures close to Tm (e.g. 51 °C), the SD structure gradually disappeared, and then the crystallization started from a single-phase mixture to yield normal crystalline structure similar to that of a neat crystalline polymer. At lower temperatures (e.g. 40 °C), crystallization quickly occurred and the SD structure was preserved, implying that the crystallization prevailed over the dissolution yielding a bi-continuous structure consisting of amorphous (SAN-rich) and crystalline (PCL-rich) regions. At intermediate temperatures (e.g. 45 °C), the phase dissolution competed with the crystallization, resulting in a bi-continuous structure with longer periodic distance and a broad boundary having a gradient in composition of amorphous region between PCL crystal lamellae. Light-scattering analysis quantitatively revealed a competition of the crystallization and the phase dissolution in terms of the crystallization rate (from Hv scattering) and the apparent diffusion coefficient for dissolution (from Vv scattering).  相似文献   

19.
Reverse micelles, Winsor III and IV systems were examined as reaction media for the enzymatic conversion of cholesterol to cholestenone by cholesterol oxidase at 298.2 K. The micelles and the microemulsions, stabilized by soybean lecithin and ethanol or 1-propanol as cosolvent, were characterized with respect to phase behavior and distribution of 1-propanol between the phases of the Winsor III systems. The used oils were dodecane, tetradecane, and hexadecane. The Winsor IV systems and the surfactant-rich phase in the Winsor III systems exhibit bicontinuous structures. The reaction yield for the enzymatic conversion performed in a Winsor IV system was much higher than in a Winsor III system or in reverse micelles.  相似文献   

20.
The synthesis and structural analysis of the twin-dendritic benzamide 10, based on the first-generation, self-assembling, tapered dendrons 3,4,5-tris(4'-dodecyloxybenzyloxy)benzoic acid and 3,4,5-tris(4'-dodecyloxybenzyloxy)-1-aminobenzene, and the polymethacrylate, 20, which contains 10 as side groups, are presented. Benzamide 10 self-assembles into a supramolecular cylindrical dendrimer that self-organizes into a columnar hexagonal (Phi(h)) liquid crystalline (LC) phase. Polymer 20 self-assembles into an imperfect four-cylinder-bundle supramolecular dendrimer, and creates a giant vesicular supercylinder that self-organizes into a columnar nematic (N(c)) LC phase which displays short-range hexagonal order. In mixtures of 20 and 10, 10 acts as a guest and 20 as a host to create a perfect four-cylinder-bundle host-guest supramolecular dendrimer that coorganizes with 10. A diversity of Phi(h), simple rectangular columnar (Phi(r-s)) and centered rectangular columnar (Phi(r-c)), superlattices are produced at different ratios between 20 and 10. This diversity of LC lattices and superlattices is facilitated by the architecture of the twin-dendritic building block, polymethacrylate, the host-guest supramolecular assembly, and by hydrogen bonding along the center of the supramolecular cylinders generated from 10 and 20.  相似文献   

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