Oleogels from Glycerol‐Based Lyotropic Liquid Crystals: Phase Diagrams and Structural Characterization

In the course of our studies on structured reverse lyotropic liquid crystals (LLC) as oleogels, a system was designed with the desired physical and rheology properties for cosmetic and pharmaceutical applications. The aqueous phase was partially replaced by glycerol to minimize bacteriological problems and obtain specific rheology characteristics. The constructed phase diagrams are based on ternary mixtures of glycerol monooleate (GMO), decane, water, and glycerol. The main lyotropic mesophase obtained in this study was reverse hexagonal derived from dilution line 8:2 (72 wt% GMO and 18 wt% decane) and 10 wt% water; or water:glycerol (wt ratios 3:1 and 1:1) mixture. It was found that heat‐cool fluctuation caused formation of new pseudo‐equilibrium structures with mesomorphic transformations to more fluid and less ordered mesostructures. Replacing up to 50 wt% of the water by glycerol significantly increases the gel phase region in the phase diagram, meaning more structural compositional options. The structural parameters were determined using cross‐polarized light microscopy (CPLM), differential scanning calorimeter (DSC), powder X‐ray diffraction (PXRD), and small angle X‐ray scattering (SAXS). Rheological measurements revealed viscoelastic properties of lyotropic liquid crystals with a decrease in the elasticity (G′), plasticity (G″), and complex viscosity (η*), as a function of increasing the glycerol content.     

Graph‐based resource allocation algorithms for multiuser downlink MIMO‐OFDMA networks

Multiuser multiple‐input multiple‐output orthogonal frequency division multiple access (MIMO‐OFDMA) is considered as the practical method to attain the capacity promised by multiple antennas in the downlink direction. However, the joint calculation of precoding/beamforming and resource allocation required by the optimal algorithms is computationally prohibitive. This paper proposes computationally efficient resource allocation algorithms that can be invoked after the precoding and beamforming operations. To support stringent and diverse quality of service requirements, previous works have shown that the resource allocation algorithm must be able to guarantee a specific data rate to each user. The constraint matrix defined by the resource allocation problem with these data rate constraints provides a special structure that lends to efficient solution of the problem. On the basis of the standard graph theory and the Lagrangian relaxation, we develop an optimal resource allocation algorithm that exploits this structure to reduce the required execution time. Moreover, a lower‐complexity suboptimal algorithm is introduced. Extensive simulations are conducted to evaluate the computational and system‐level performance. It is shown that the proposed resource allocation algorithms attain the optimal solution at a much lower computational overhead compared with general‐purpose optimization algorithms used by previous MIMO‐OFDMA resource allocation approaches. Copyright © 2012 John Wiley & Sons, Ltd.     

Making Nonwoven Fibrous Poly(ε‐caprolactone) Constructs for Antimicrobial and Tissue Engineering Applications by Pressurized Melt Gyration

A pressurized melt gyration process has been used for the first time to generate poly(ε‐caprolactone) (PCL) fibers. Gyration speed, working pressure, and melt temperature are varied and these parameters influence the fiber diameter and the temperature enabled changing the surface morphology of the fibers. Two types of nonwoven PCL fiber constructs are prepared. First, Ag‐doped PCL is studied for antibacterial activity using Gram‐negative Escherichia coli and Pseudomonas aeruginosa microorganisms. The melt temperature used to make these constructs significantly influences antibacterial activity. Neat PCL nonwoven scaffolds are also prepared and their potential for application in muscular tissue engineering is studied with myoblast cells. Results show significant cell attachment, growth, and proliferation of cells on the scaffolds.

     

Electrochemistry of Organic Cations. VI. Investigations about the Cathodic Cleavage of Some Pyridinium and Triazolium Ions

The electrochemical reduction of some N-acylamino-, N-amino-, N-benzyl- and N-phenacyl-substituted pyridinium and triazolium ions is investigated in acetonitrile by voltammetric methods and potentiostatic electrolyses. The acylaminopyridinium ions 1 and the arylaminopyridinium ions 3 are cathodically cleaved into the pyridine derivative and the carboxylic amide or the aromatic amine. In the case of the 1-benzyl-4-acylaminotriazolium ions 5 the reductive formation of hydrogen from the acidic N-acylamino group is preferred and the corresponding ylide is formed, which reacts at more negative potential by splitting off the benzyl group. The reduction of the N-phenacylpyridinium ion 7d occurs with splitting off the phenacyl radical, which dimerizes to 1,2-dibenzoylethane in a good yield. In the case of N-benzyl- and N-p-cyanobenzylpyridinium ions the cathodic dimerization to the corresponding bisdihydropyridines was found, whereas the electrolysis of the N-nitrobenzylpyridinium ions occurs with cleavage of the N-substituent-bond, which is initiated by the primary formation of the nitrophenyl anion radical. It follows from electrogenerated chemiluminescence experiments that the cleavage of the cations 1 and 5 occurs with the uptake of one electron.     

Photochemie substituierter Cycloheptatriene. XV. Zur Charakterisierung der Elektronischen Übergänge in 1-Aryl-4-(p-dimethylaminophenyl)-cycloheptatrienen

Photochemistry of Substituted Cycloheptatrienes. XV. About the Characterization of the Electronic Transitions in 1-Aryl-4-(p-dimethylaminophenyl)-cycloheptatrienes The absorption spectra of the title compounds are discussed in dependence on polarity of the solvent and its ability to form hydrogen bonds. The results suggest a hybridization of the N-atom of the dimethylamino group between sp³ and sp² in the ground state. Contrary to this, the nitrogen has sp²-hybridization in the short wavelength (SE) fluorescing state. In a second fluorescence state the geometry of the seven-membered ring should change. Therefore the viscosity of the solvents influences both the position and the quantum yield of this long wavelength emission (LE). The influence of polarity and viscosity of the solvents is described by multiple regression. The temperature dependence of fluorescence quantum yields is discussed, as well.     

Stabilization of Paste Viscosity of Cassava Starch by Heat Moisture Treatment

Cassava starch has poor paste stability during prolonged cooking. The starch was modified by heat moisture treatment. A premoistured starch (18–24% moisture) was subjected to heat treatment for 3–16h to bring about paste stability. Different types of heat treatments like moist pressure heating, dry heating and microwave heating was tried. The optimum heat treatment to bring about the paste stability was found to be 18–21% premoistured starch, which was heated at 110°C per 16h. The modified starch granules were intact and had comparatively increased sedimentation volume, oil binding capacity, amylase susceptibility, and decreaced crystallinity, water binding capacity, solubility and paste translucency. The freeze - thaw stability was excellent with modified cassava starch. “Pie filling and Halwa” (an Indian sweetmeat) made from modified cassava starch had good organoleptic properites.     

Photochemie von Acylaziden. VIII [1]. Reagieren Acylnitrene wie 1,3-Dipole??

Photochemistry of Acylazides. VIII. Do Acylnitrenes React like 1,3-Dipoles? The formation of three- ore five-membered heterocyclic rings by the reaction of acylnitrenes with olefins depends on the electron density at the double bond. The generally expected formation of aziridines by a cheletropic reaction was observed by photolysis of aroylazides 1 in the presence of 2,5-dihydrofuran 2 . But with enolethers 3 and 4 oxazolines were directly formed. This [3 + 2] cycloaddition is regiospecific. The cycloaddition is modestly stereoselective by steric hindrance within the cyclic enolether 3b . Very small de-values were found with chiral substituents in the acylazide 13 . The azide decomposition was also achieved by photoinduced electron transfer. The same cycloaddition products as obtained by direct photolysis of the azides were obtained via radical anions of the acylazide. Using Michler's ketone as electron donor in the triplet state the formation of isocyanate which diminishes the yield of cycloadducts can be avoided.     

Transport and solvent sensing characteristics of styrene butadiene rubber nanocomposites containing imidazolium ionic liquid modified carbon nanotubes

Obtaining strong interfacial interaction between filler and polymer matrix is very crucial for the fabrication of polymer nanocomposites with superior performance. Present study is aimed to fabricate high performance styrene butadiene rubber (SBR) nanocomposites with imidazolium type ionic liquid modified multiwalled carbon nanotube (MWCNT). Ionic liquid facilitates the dispersion of MWCNT in rubber matrix and it is obvious from transmission electron microscopy images. Diffusion of toluene through SBR nanocomposite membranes has been investigated as a function of surface modified MWCNT (f-MWCNT) content to analyze the chain dynamics and filler-polymer interactions. O₂ gas barrier effect of nanocomposites with special reference to the filler loading is explored. The substantial improvement in the barrier effect in presence of filler interpreted on the grounds of a theoretical model describing permeability of heterogeneous systems. Finally solvent sensing characteristics of prepared nanocomposites are also analyzed and it is observed that prepared nanocomposites can be used as a flexible solvent sensor.     

Dietary alteration of fatty acid composition of lipid classes in mouse mammary adenocarcinoma

The composition of total fatty acids in serially transplanted mammary adenocarcinomas of C3H mice which were fed a fat free diet or a stock diet containing 4% fat for 8 weeks were significantly different, although fatty acid amounts were similar. The difference in composition was manifested in the triglyceride, phosphatidyl choline, and phosphatidyl enthanolamine fractions. Tumors of mice fed fat free diet has appreciable amounts of eicosatrienoic acid, whereas neoplasms of stock diet fed animals had none. In addition, higher levels of oleic acid and lower contents of linoleic acid were found in tumors from mice fed fat free diet than in those from mice fed the stock diet. Thus, mechanisms which maintained the triglyceride fatty acid composition in some tumors, such as 7288CTC hepatoma, were not observed in mouse mammary adenocarcinomas, and, therefore, were not a general phenomena associated with carcinogenesis.