Synthesis of Well-Defined Oligo(2,5-dialkoxy-1,4-phenylene vinylene)s with Chiral End Groups: Unique Helical Aggregations Induced by the Chiral Chain Ends.

Oligo(2,5-dialkoxy-1,4-phenylenevinylene)s containing three different chiral alkoxy substituents on the phenyl end groups with structurally regular (all trans) controlled repeat units have been prepared; these compounds showed highly enhanced aggregation-induced circular dichroism (AICD; formation of supramolecular polymers), and an inversion of the CD signal was observed even with the same end groups under certain conditions.

Competitive surfactant adsorption of AOT and Tween 20 on gold measured using a quartz crystal microbalance with dissipation.

Competitive surfactant adsorption of anionic surfactant AOT and nonionic surfactant Tween 20 on gold was investigated by using a quartz crystal microbalance with dissipation (QCM-D) at 25 °C. The adsorption isotherm of pure AOT did not reach a plateau at the CMC, but rather adsorption continued to increase gradually at concentrations higher than the CMC before reaching a plateau. This behavior is evidence of competitive adsorption between AOT and impurities. The adsorbed layer of AOT on gold became more viscoelastic as the concentration of AOT increased. Tween 20 reached the plateau adsorption on gold before its concentration reached the CMC, suggesting that the attraction between Tween 20 and gold is very strong. The Tween 20 adsorbed layer was rigid when compared to the AOT adsorbed layer, as indicated by low dissipation. The addition of Tween 20 to a surface covered by AOT resulted in an increase in adsorbed mass, suggestive of the insertion of Tween 20 into the AOT adsorbed layer as expected because Tween 20 is able to separate the repulsive headgroups of AOT. When AOT was added to a preformed Tween 20 layer, a drop in the adsorbed amount was found between 0 and 0.1 CMC, and then no change was observed until the CMC of AOT was reached; the adsorbed amount then increased, reaching a final adsorption greater than that of pure AOT. All data support the formation of mixed surfactant layers on the surface. Although a two-step model fit both AOT and Tween 20 adsorption kinetic data well, AOT was found to adsorb much more slowly than Tween 20.

High Conversion of CaO-Catalyzed Transesterification of Vegetable Oils with Ethanol.

Fatty acid ethyl esters (FAEEs) derived from vegetable oils and ethanol are promising bio-based chemicals for various applications such as biofuel, monomers for polyesters, and fine chemicals. However, the limited conversion and yield are obtained in the conventional methods due to low boiling point of ethanol that thus requires conducting the reaction at low temperature. This work demonstrates high yield of FAEEs from soybean, rice bran and palm oil with ethanol by performing the transesterification at high temperatures of 150-200°C by using CaO catalyst in a high pressure reactor. The results demonstrate the complete reaction for all vegetable oils with low ethanol to oil molar ratio of 6:1 and 1 wt.% CaO catalyst. Higher reaction temperature results in faster reaction while keeping high conversion of ≥ 99.0%. The unsaturated components in FAEE products are consistent with their original fatty acid chain. Moreover, the high conversion can be achieved even in the reaction conducted with low ethanol to oil molar ratio of 4.5:1 and 0.5 wt.% CaO catalyst at 180 °C in the palm oil transesterification. The catalyst can be reused for at least 3 times with the conversion higher than 94.0%. In addition, the activation energy (Ea), enthalpy of activation (ΔH‡), entropy of activation (ΔS‡) and Gibbs free energy of activation (ΔG‡) are also obtained.

Roles of Sodium Dodecyl Sulfate on Tetrahydrofuran-Assisted Methane Hydrate Formation.

Sodium dodecyl sulfate (SDS) markedly improved tetrahydrofuran (THF) - assisted methane hydrate formation. Firstly, methane hydrate formation with different THF amount, 1, 3, and 5.56 mol%, was studied. SDS with 1, 4, and 8 mM was then investigated for its roles on the methane hydrate formation with and without THF. The experiments were conducted in a quiescent condition in a fixed volume crystallizer at 8 MPa and 4°C. The results showed that almost all studied THF and SDS concentrations enhanced the methane hydrate formation kinetics and methane consumption compared to that without the promoters, except 1 mol% THF. Although, with 1 mol% THF, there were no hydrates formed for 48 hours, the addition of just 1 mM SDS surprisingly promoted the hydrate formation with a significant increased in the kinetics. This prompts the use of methane hydrate technology for natural gas storage application with minimal promoters.

Pyrolytic characteristics of sewage sludge.

In this study, a number of different sewage sludge including sludge samples from industrial and hospital wastewater treatment plants were characterized for pyrolysis behavior by means of thermogravimetric analysis up to 800 degrees C. According to the thermogravimetric results, five different types of mass loss behaviors were observed depending on the nature of the sludge used. Typical main decomposition steps occurred between 250 and 550 degrees C although some still decomposed at higher temperatures. The first group (Types I, II and III) was identified by main decomposition at approximately 300 degrees C and possible second reaction at higher temperature. Differences in the behavior may be due to different components in the sludge both quantitatively and qualitatively. The second group (Types IV and V), which rarely found, has unusual properties. DTG peaks were found at 293, 388 and 481 degrees C for Type IV and 255 and 397 degrees C for Type V. Kinetics of sludge decomposition can be described by either pseudo single or multicomponent overall models (PSOM or PMOM). The activation energy of the first reaction, corresponding to the main pyrolysis typically at 300 degrees C, was rather constant (between 68 and 77 kJ mol(-1)) while those of second and third reactions were varied in the range of 85-185 kJ mol(-1). The typical order of pyrolysis reaction was in the range of 1.1-2.1. The pyrolysis gases were composed of both saturated and unsaturated light hydrocarbons, carbon dioxide, ethanol and chloromethane. Most products, however, evolve at a quite similar temperature regardless of the sludge type.

Synthesis and structural analysis of tungsten-carbonyl dimers bridged with oligo(2,5-dialkoxy-1,4-phenylene vinylene)s through pyridine coordination.

Tungsten carbonyl dimers bridged with oligo(2,5-dialkoxy-1,4-phenylene vinylene)s through coordination with pyridine as the end groups, expressed as [W(CO)5]2-(nPV-Py2) [n = 1, 3; alkoxy = O(CH2)2OSi(i)Pr3], have been prepared from W(CO)5(THF) with nPV-Py2 in THF, and their structures were determined by X-ray crystallography. Both increase in absorbance and redshift in the λmax values in [W(CO)5]2-(nPV-Py2) from their nPV-Py2 were observed in the UV-vis spectra, due to increase in the conjugation length through tungsten by coordination of the pyridine moiety; an extension of the conjugation was also confirmed by the crystallographic analysis as well as fluorescence spectra.

Physicochemical properties of oleic acid-based partially fluorinated gemini surfactants.

We have developed oleic acid-based partially fluorinated gemini surfactants with carboxylic acid headgroups. The fluorocarbon chain is covalently bound to the terminal carbonyl group of oleic acid via a -CH(2)CH(2)OCO- unit, and the carboxylic acid headgroups are introduced to the cis double bond of oleic acid via -OCOCH(2)CH(2)- units. The aqueous solution properties of these surfactants were studied at pH 9 in the presence of 10 mmol dm­3 NaCl by means of static surface tension, pyrene fluorescence, and dynamic light scattering measurements. The resulting surface tension data demonstrate that the partially fluorinated gemini surfactants exhibit excellent surface activity in their dilute aqueous solutions. In addition, the surfactants are suggested to form micellar aggregates 2­4 nm in diameter. We also studied the aqueous temperature-concentration phase diagrams of the partially fluorinated gemini surfactants (disodium salts) on the basis of visual observations (through a crossed polarizer), polarized optical microscopy, and small angle X-ray scattering measurements. Several phase states including micellar solution phase, hexagonal phase, bicontinuous cubic phase, and lamellar phase were observed along with the coexistence of these phases in certain regions. Assemblies with lesser positive curvature tend to be formed with increasing surfactant concentration, increasing temperature, and increasing fluorocarbon chain length. A comparison of the phase diagrams of the partially fluorinated and hydrogenated surfactant systems suggests that close molecular packing is inhibited within the assemblies of the partially fluorinated surfactants because of the limited miscibility between the fluorocarbon and hydrocarbon units. To the best of our knowledge, this is the first systematic report focusing on the temperature-concentration phase diagrams of (partially) fluorinated gemini surfactants over a wide range of compositions and temperatures.

Quaternary ammonium-type gemini surfactants synthesized from oleic acid: aqueous solution properties and adsorption characteristics.

Cationic gemini surfactants having a quaternary ammonium headgroup have been synthesized from oleic acid. The hydrocarbon chain is covalently bound to the terminal carbonyl group of oleic acid via an amide bond, while the quaternary ammonium headgroup is introduced onto the cis double bond of oleic acid. The Krafft temperature of these surfactants drops below room temperature (ca. 25°C) when the counterion is exchanged from Br⁻ to Cl⁻. The aqueous solution properties of the Cl series of surfactants have been assessed by means of pyrene fluorescence, dynamic light scattering (DLS), and static surface tension measurements. An increased hydrocarbon chain length results in a lower critical micelle concentration (cmc) and a higher adsorption efficiency at the air/aqueous solution interface. Surface tension measurements suggest the formation of premicelles at concentrations below cmc, whereas, above cmc, DLS indicates the formation of micellar aggregates whose diameter ranges from 5 to 10 nm. We, furthermore, characterized the adsorption of these surfactants to the silica/aqueous solution interface and observed their spontaneous adsorption to the solid surface by electrostatic and intermolecular hydrophobic interactions. The combination of soft-contact imaging atomic force microscopy (AFM) and force-curve data suggests bilayer formation above cmc, which is reflective of the large packing parameter of the gemini surfactants. Interestingly, we found the repulsive interaction observed during compression of the adsorbed layer to be relatively weak, as a result of the low adsorption density and/or the loose molecular packing arrangement, which arises from the asymmetric structure.