Characterizing Colloidal Structures of Pseudoternary Phase Diagrams Formed by Oil/Water/Amphiphile Systems

Two pseudoternary phase diagrams were constructed using ethyl oleate, water, and a surfactant blend containing poly (oxyethylene 20) sorbitan monooleate and sorbitan monolaurate with or without the cosurfactant 1-butanol. Two colloidal regions were identified in the cosurfactant-free phase diagram; a microemulsion (ME) and a region containing lamellar liquid crystals (LC). The addition of 1-butanol increased the area in which systems formed microemulsions and eliminated the formation of any liquid crystalline phases. Samples that form the colloidal regions of both systems were investigated by freeze-fracture transmission electron microscopy and by viscosity and conductivity measurements. The three techniques were compared and evaluated as characterisation tools for such colloidal systems and also to identify transitions between the colloidal systems formed. A droplet ME was present at a low water volume fraction (?_w) in both systems (?_w <0.15) as revealed by electron microscopy. At higher ?_w values, LC structures were observed in micrographs of samples taken from the cosurfactant-free system while the structure of samples from the cosurfactant-containing system was that of a bicontinuous ME. The viscosity of both systems increased with increasing ?_w to 0.15 and flow was Newtonian. However, formation of LC in the cosurfactant-free system resulted in a dramatic increase in viscosity that was dependent on ?_w and a change to pseudoplastic flow. In contrast, the viscosity of the bicontinuous ME was independent of ?_w. Three different methods were used to estimate the percolation threshold from the conductivity data for the cosurfactant-containing system. The use of nonlinear curve fitting was found to be most useful yielding a value close to 0.15 for the ?_w.     

提高AEO9/醇/烷/水体系反相微乳液陶瓷墨水浓度的研究

鉴于陶瓷墨水在某些性能上存在不足,例如相对连续式喷墨打印机打印成型要求而言粘度较大、电导率偏低、固相含量不够高等问题,通过加入醇和Na₂CO₃等添加剂以及利用双连续结构分别对粘度、电导率等性能加以调整及提高陶瓷墨水的浓度。少量醇的加入(1％～2％)使陶瓷墨水体系粘度降低到11mPa·S左右,根据相图从双连续结构角度出发设计了陶瓷墨水的组成,考察了溶水量的变化,并借以提高陶瓷墨水固相含量,使其达到2.54％。由于双连续结构陶瓷墨水的理化性能(粘度、电导率等)仍不能完全满足要求,加入少量Na₂CO₃进行改性,改性后的陶瓷墨水粘度降至18mPa·s以下,电导率接近100mS/m,稳定性良好,墨水中陶瓷颗粒粒度在10nm以下,但透光率略有降低,显微结构观察表明具有明显的双连续结构特征。     

Thermal conductivity of liquid crystalline epoxy/BN filler composites having ordered network structure

BN filler was added to a liquid crystalline (LC) epoxy resin to obtain a high thermal conductive material. The LC epoxy/BN composites, which were cured at different temperatures, formed an isotropic or LC polydomain phase structure. The relationship between the network orientation containing mesogenic groups and the dispersibility of the BN filler was discussed. As a result, the thermal conductivity of the LC polydomain system was drastically enhanced even at a relatively low volume fraction of BN (30 vol%), regardless of the fact that both the LC and isotropic phase systems consisted of the same resin and filler content combination. This result is due to the formation of thermal conductive paths by the BN filler by exclusion of the BN filler from the LC domain formed during the curing process in the composite having the LC polydomain matrix.     

Formation and Stability Studies of Multiple (w/o/w) Emulsions Prepared with Newly Synthesized Rosin-Based Polymeric Surfactants

The multiple (water-in-oil-in-water, w/o/w) emulsions were prepared using newly synthesized rosin-based polymeric surfactants. The oil phase used was liquid paraffin. These emulsions were evaluated for stability by various methods: conductivity, viscosity, particle size, and visual inspection. The stability studies were carried out at 37°C and 4°C for 1 month. The multiple emulsion prepared with polymer 7 was found to be more stable compared to the emulsions prepared with polymer 2.     

Formation and stability studies of multiple (w/o/w) emulsions prepared with newly synthesized rosin-based polymeric surfactants

The multiple (water-in-oil-in-water, w/o/w) emulsions were prepared using newly synthesized rosin-based polymeric surfactants. The oil phase used was liquid paraffin. These emulsions were evaluated for stability by various methods: conductivity, viscosity, particle size, and visual inspection. The stability studies were carried out at 37°C and 4°C for 1 month. The multiple emulsion prepared with polymer 7 was found to be more stable compared to the emulsions prepared with polymer 2.     

Formulation and characterization of liquid crystal systems containing azelaic acid for topical delivery

Purpose: The aim of this study is to prepare and characterize azelaic acid (AzA) containing liquid crystal (LC) drug delivery systems for topical use.

Methods: Two ternary phase diagrams, containing liquid paraffin as the oil component and a mixture of two nonionic surfactants (Brij 721P and Brij 72), were constructed. Formulations chosen from the phase diagrams were characterized by polarized light microscopy, rheological analyses, differential scanning calorimetry (DSC), and small angle x-ray scattering spectroscopy.

Results: Polarized light microscopy proved that except the oil/water emulsion (O/W E), other formulations showed lamellar LC structure. In vitro release studies indicated that the fastest release was achieved by the Lamellar LC (LLC) and O/W E systems, whereas slower release was obtained from the emulsion containing lamellar LC (E-LLC) and distorted lamellar LC (D-LLC) systems. Results of rheological measurements both supported the results of in vitro release studies and showed that the emulsion containing the LC (E-LLC) system had the most stable structure. The formulations and their effect on stratum corneum (SC) were evaluated by DSC studies. The lamellar LC (LLC), emulsion containing lamellar liquid crystal (E-LLC), and O/W E formulations had an effect on both lipid and protein components of SC, whereas distorted lamellar liquid crystal (D-LLC) system had an effect on only the lipid components of SC.

Conclusions: LLC systems could be considered promising for the topical delivery of AzA.     

甲基丙烯酸/衣康酸/烯丙基磺酸盐超分子分散剂的合成与性能表征

衣康酸(IA)、烯丙基磺酸钠(SAS)和甲基丙烯酸(ME)可通过自由基共聚反应制备具有两亲结构的水溶性超分子分散剂(SPMIS),文中通过对浆料的黏度、流变性进行表征得到了分散剂的最佳合成条件:单体配比为w(衣康酸)∶w(烯丙基磺酸钠)∶w(甲基丙烯酸)=1.0∶1.0∶1.3,反应温度为70℃。并对聚合物分散剂的结构和性质进行了分析,同时对粘土浆料的流变性和SEM图进行了研究,结果表明,分散剂中含有大量的-OH、-SO3H,当添加量为0.40%(相对绝干料的质量分数)时,分散效果最好。     

Optical and electrical characterization of a gold nanoparticle dispersion in a chiral liquid crystal matrix

We report on the effect of gold nanoparticle (Au NP) dispersion in a chiral nematic liquid crystal (LC). Polarized optical microscopy and X-ray diffraction measurements evidence the insurgence of an order change in the LC host. Moreover, a comparative analysis based on dielectric and voltammetric spectroscopies performed on pure LC and on Au NP-doped LC shows that Au NP’s presence besides affecting LC order influences its electric properties: ion conductivity results importantly reduced, and beyond a threshold value of the applied field electrophoresis phenomena are induced.     

Hierarchical assembly of carbon nanotubes-liquid crystal nanocomposite

Fabrication of liquid crystalline (LC) nanomaterials in an aligned pattern along the multiwalled carbon nanotubes (CNT) has been reported here. The nanocomposite was prepared by sonicating esterified CNTs and the ferroelectric liquid crystal (FLC) in chloroform. The nanohybrid shish kebab (NHSK) like pattern was observed in SEM analysis. The nanocomposite materials were characterized by Fourier transform infrared spectroscopy (FTIR), polarizing optical microscopy and electron microscopy. The DC and AC electrical properties of the composite materials were investigated. The DC conductivity of the nanocomposite increased by 2 order from the FLC materials and AC relaxation has been observed, in the nanocomposite, which was totally absent in the FLC materials.     

Three-dimensional metal scaffold supported bicontinuous silicon battery anodes

Silicon-based lithium ion battery anodes are attracting significant attention because of silicon's exceptionally high lithium capacity. However, silicon's large volume change during cycling generally leads to anode pulverization unless the silicon is dispersed throughout a matrix in nanoparticulate form. Because pulverization results in a loss of electric connectivity, the reversible capacity of most silicon anodes dramatically decays within a few cycles. Here we report a three-dimensional (3D) bicontinuous silicon anode formed by depositing a layer of silicon on the surface of a colloidal crystal templated porous nickel metal scaffold, which maintains electrical connectivity during cycling due to the scaffold. The porous metal framework serves to both impart electrical conductivity to the anode and accommodate the large volume change of silicon upon lithiation and delithiation. The initial capacity of the bicontinuous silicon anode is 3568 (silicon basis) and 1450 mAh g(-1) (including the metal framework) at 0.05C. After 100 cycles at 0.3C, 85% of the capacity remains. Compared to a foil-supported silicon film, the 3D bicontinuous silicon anode exhibits significantly improved mechanical stability and cycleability.     

A modern approach for controlled transdermal delivery of diflunisal: optimization and in vivo evaluation

The purpose of the present work was to elaborate an optimized transdermal therapeutic system for diflunisal. Selection of suitable ingredients was done via solubility and phase behavior studies. Composition of microemulsion (ME) systems consisting of butyl lactate, Brij^® 97, Transcutol^® and water was optimized using augmented simplex lattice mixture design. The independent variables selected were the percentages of butyl lactate, surfactant mixture and water. The dependent variables were refractive index, pH, conductivity, viscosity, drug solubility in the ME formulation and the ex vivo skin permeation flux. Mathematical equations and response surface plots were used to relate the dependent and independent variables. The statistical validity of the polynomials was established. Optimized formulation factors were selected by desirability approach. The optimized ME formulation was converted into gel using Carbomer^® 934. The microemulsion based gel (MBG) showed better spreadability and 5.07-fold increase in the transdermal flux than Carbomer^® 934 gel. The in vivo antihyperalgesia assay performed on mice showed significant reduction of the licking time in the treated group compared to the control group. This demonstrated the reliability of the simplex lattice statistical design for predicting optimum ME formulation. The developed MBG proved its in vivo efficiency for transdermal delivery of diflunisal.     

Enhancement of the skin permeation of clindamycin phosphate by Aerosol OT/1-butanol microemulsions

Microemulsions of water/isopropyl palmitate (IPP)/Aerosol OT (AOT)/1-butanol were developed as alternative formulations for topical delivery of clindamycin phosphate. Effect of AOT:1-butanol ratios on microemulsion region existence in the pseudoternary phase diagrams was investigated. The 2:1 AOT:1-butanol provided the largest microemulsion region. Five microemulsions of 1% w/w clindamycin phosphate were prepared and characterized. The permeation through human epidermis of the microemulsions was evaluated and compared with the 70% isopropanol solution using modified Franz diffusion cells. The drug permeation from all microemulsions was found to be significantly greater than that from the solution, indicating the enhancement of the skin permeation by the microemulsions. Within the same microemulsion type, the drug permeation increased with increasing the amount of AOT:1-butanol. The drug permeation from oil-in-water (o/w) microemulsions was relatively higher than that from water-in-oil (w/o) microemulsions. In addition, all microemulsions were stable for at least three months at 30 ± 1°C.     

电导法对CTAB／正丁醇／环己烷／水四组分微乳体系的研究

利用电导率（K）-增溶水量（ml）关系曲线研究了CTAB／正丁醇／环己烷／水四组分微乳体系在不同增溶水量时的3种结构，即油包水（W／O）、油水双连续（BC）、水包油（O／W）。讨论了表面活性剂CTAB与助表面活性剂正丁醇不同浓度时对微乳液稳定性的影响，得出了微乳液稳定时CTAB和正丁醇的合适配比。     

Enhancement of the Skin Permeation of Clindamycin Phosphate by Aerosol OT/1-Butanol Microemulsions

Microemulsions of water/isopropyl palmitate (IPP)/Aerosol OT (AOT)/1-butanol were developed as alternative formulations for topical delivery of clindamycin phosphate. Effect of AOT:1-butanol ratios on microemulsion region existence in the pseudoternary phase diagrams was investigated. The 2:1 AOT:1-butanol provided the largest microemulsion region. Five microemulsions of 1% w/w clindamycin phosphate were prepared and characterized. The permeation through human epidermis of the microemulsions was evaluated and compared with the 70% isopropanol solution using modified Franz diffusion cells. The drug permeation from all microemulsions was found to be significantly greater than that from the solution, indicating the enhancement of the skin permeation by the microemulsions. Within the same microemulsion type, the drug permeation increased with increasing the amount of AOT:1-butanol. The drug permeation from oil-in-water (o/w) microemulsions was relatively higher than that from water-in-oil (w/o) microemulsions. In addition, all microemulsions were stable for at least three months at 30 ± 1°C.     

Bicontinuous water-AOT/Tween85-isopropyl myristate microemulsion: a new vehicle for transdermal delivery of cyclosporin A

The purpose of this study was to investigate the influence of structure and composition of microemulsions (AOT/Tween85/isopropyl myristate/water) on their transdermal delivery potential of a lipophilic model drug (Cyclosporin A), and to compare the drug delivery potential of microemulsion to the suspension of drug in normal saline containing 20% ethanol. Their type and structure were examined by measuring surface tension, density, viscometry, and electric conductivity; the degree of agreement between the techniques was assessed. Transdermal flux of Cyclosporin A through rat skin was determined in vitro using Franz-type diffusion cells. Results of conducting, viscosity, and surface tension measurement confirmed the prediction transition to a bicontinuous structure. The microemulsions increased transdermal drug delivery of Cyclosporin A up to 10 times compared to the suspension. The increased transdermal delivery was found to be due mainly to water concentration and appeared to be dependent on the structure of the microemulsions.     

Experimental Determination of Densities and Isobaric Vapor–Liquid Equilibria of Methyl Acetate and Ethyl Acetate with Alcohols (C3 and C4) at 0.3 MPa

The densities and excess volumes were determined at 298.15 K for the methyl acetate + 1-propanol, methyl acetate + 1-butanol, and ethyl acetate + 1-butanol mixtures. The vapor–liquid equilibria data at 0.3 MPa for these binary systems were obtained using a stainless steel equilibrium still. The activity coefficients were obtained from the experimental data using the Hayden and O’Connell method and the Yen and Woods equation. The binary systems in this study showed positive deviations from ideality. The experimental VLE data were verified with the point-to-point test of van Ness using the Barker routine and the Fredenslund criterion. The different versions of the UNIFAC and the ASOG group contribution models were applied.     

Evaluation of the methylene blue addition in binary polymeric systems composed by poloxamer 407 and Carbopol 934P using quality by design: rheological,textural, and mucoadhesive analysis

This study describes the investigation about the physicochemical behavior of methylene blue (Mb) addition to systems containing poloxamer 407 (Polox), Carbopol 934P (Carb), intended to be locally used by photodynamic therapy. A factorial design 2³ (plus center point) was used to analyze the rheological, mucoadhesive and textural properties of the preparations. Systems containing the lower concentrations of Polox (15 and 17.5%, w/w) exhibited pseudoplastic flow and low degrees of rheopexy. On the other hand, at higher Polox concentration (20%, w/w) the systems display plastic flow and thixotropy. Carb and Mb exhibited a negative influence for the consistency and flow behavior index, due to the interaction between them. For most of the formulations, the increase of Polox and Mb content significantly increased storage modulus, loss modulus and dynamic viscosity. The systems display a sol–gel transition temperature, existing as a liquid at room temperature and gel at 29–37?°C. Increasing the temperature and the polymer concentration, the compressional properties of systems significantly increased. The mucoadhesion was noted to all formulations, except to systems composed by 15% (w/w) of Polox. The analyses enabled to understand and predict the performance of formulations and the polymer–Mb interactions, tailoring to the suit systems (Polox/Carb/Mb): 17.5/0.50/0.20 and 20/0.15/0.25.     

Confocal laser scanning microscopy: Applications in material science and technology

Confocal laser scanning microscope (CLSM) has great advantage over a conventional microscope because it rejects the light that does not come from the focal plane, enabling one to perform optical slicing and construction of three-dimensional (3D) images. Further its high axial resolution, sharp image quality and associated quantitative image analysis provide vital structural information in the mesoscopic range for the full 3D realization of the microstructure. Because of this unique feature, CLSM is now finding wider applications in the study of variety of materials and processes such as phase separation in binary polymer mixtures, fracture toughness in alloys, in determining residual strains in fibre-reinforced metal composites, and in microvisualization of corrosion. This paper reviews some of these recent applications and also discusses our results on colloidal dispersions. CLSM has been used to characterize the amorphous structure in highly-charged colloidal systems which have undergone gas-solid transition. CLSM images show presence of large voids deep inside the disordered suspensions. Frame averaged images reveal that the structural disorder is amorphous. The reasons for voids coexisting with dense amorphous regions and their implications on colloidal interactions are discussed. The article also reviews the use of fluorescence-CLSM in the investigation of novel materials of technological importance such as template-directed colloidal crystals with preferred orientations and multilayered structures with different crystal plane symmetries. Direct measurement of the interfacial curvatures for a bicontinuous polymer blend system as well as real space measurement of structure in phase separating polymer mixtures are now possible using CLSM. This paper reviews some of these results highlighting the unique advantages of confocal microscopy for better understanding of the microstructure and mechanistic aspects of various important phenomena in a large variety of materials.     

Bicontinuous Water-AOT/Tween85-Isopropyl Myristate Microemulsion: A New Vehicle for Transdermal Delivery of Cyclosporin A

ABSTRACT

The purpose of this study was to investigate the influence of structure and composition of microemulsions (AOT/Tween85/isopropyl myristate/water) on their transdermal delivery potential of a lipophilic model drug (Cyclosporin A), and to compare the drug delivery potential of microemulsion to the suspension of drug in normal saline containing 20% ethanol. Their type and structure were examined by measuring surface tension, density, viscometry, and electric conductivity; the degree of agreement between the techniques was assessed. Transdermal flux of Cyclosporin A through rat skin was determined in vitro using Franz-type diffusion cells. Results of conducting, viscosity, and surface tension measurement confirmed the prediction transition to a bicontinuous structure. The microemulsions increased transdermal drug delivery of Cyclosporin A up to 10 times compared to the suspension. The increased transdermal delivery was found to be due mainly to water concentration and appeared to be dependent on the structure of the microemulsions.     

Aspirin Degradation in Mixed Polar Solvents

Degradation studies were conducted on 0.2% w/v aspirin liquid formulation in a wide range of water-propylene glycol mixtures and water-triethylene glycol diacetate mixtures at four temperatures. The effect of a surfactant, polyoxyethylene (20) sorbitan monolaurate, on aspirin stability was also investigated. There was a linear relationship between water content and degradation rate constants. The surfactant increased aspirin degradation in all formulations. Formulations containing the higher concentration of the surfactant showed the greater aspirin decomposition.