Aqueous solution properties of disulfide-linked fluorinated gemini and cleaved monomeric thiol surfactants

We prepared a fluorinated gemini surfactant containing a disulfide bond in its spacer chain, [C?F??(CH?)?N(CH?)?CH?CH?SSCH?CH?N(CH?)?(CH?)?C?F??]2Cl, and its analogue with a hexamethylene spacer. Monomeric thiol surfactant, [C?F??(CH?)?N(CH?)?CH?CH?SH]Cl, was readily produced by the cleavage of the gemini surfactant using dithiothreitol in water. The critical micelle concentration was determined using surface tension, conductivity, and fluorescence probe methods. The critical micelle concentration of the monomeric surfactant was significantly larger than that of the gemini surfactant. The surface tension of aqueous solution for the cleaved monomeric thiol surfactant returned gradually to the original value through the formation of the disulfide bond via air oxidation.     

Aqueous solution behavior of cationic surfactants containing sulfide linked alkyl chain

Cationic surfactants containing a thioether group in the hydrophobic chain were prepared by the reaction of alkanethiol and bromocholine bromide. The aqueous solution properties of the thio-surfactants were investigated and compared with conventional cationic surfactants. The Krafft temperatures of the thio-surfactants were lower than that of alkyltrimethylammonium bromide. The critical micelle concentrations were determined by the conductivity method, and pyrene and SPQ fluorescence probe methods. A linear relation was observed for the plots of cmc vs. chain length. However, the cmc of the thio-surfactants depended on the position of the thioether group in the hydrophobic alkyl chain. It was found that the thioether group exhibited quenching ability toward SPQ fluorescence. The variation of the surfactant monomer concentration in equilibrium with micelles can be estimated from Stern-Volmer plots.     

Double layer capacitance of high surface area carbon nanospheres derived from resorcinol–formaldehyde polymers

Micro-mesoporous bimodal carbon nanospheres with high surface areas were synthesized by a combined use of surfactant templating technique and BaO₂ chemical activation one. Starting spherical nanopolymer/surfactant composites were prepared by the NaOH-catalyzed reaction of resorcinol (R) and formaldehyde (F) in the presence of cetyltrimethylammonium bromide (CTAB) as a core template and 1,3,5-trimethylbenzene (TMB) and tert-butanol (t-BuOH) as cosurfactants. After pretreatment with hydrochloric acid, the composite materials were calcined at 1000 °C in N₂ coexistent with varying weight ratios of BaO₂ to RF polymer ranging from 0 to 11. It produced micro-mesoporous bimodal carbon nanospheres of 124–143 nm diameter, with specific surface areas as high as 1884 m² g⁻¹ or up to 3301 m² g⁻¹, in contrast to microporous ones with smaller surface areas obtained at low BaO₂-loadings. The electrochemical double layer capacitance of the resulting nanocarbons in 0.5 M H₂SO₄ showed a marked increase with specific surface areas, up to as high as 219 F g⁻¹ for the highest surface area carbon material.     

Determination of optical purity and absolute configuration of natural 12‐hydroxystearic acid by the 1H NMR anisotropy method

The enantiopure of (R)‐(?) MαNPA was allowed to react with racemic 18‐(tert‐butyldimethylsilyloxy)‐5‐octadecayne‐7‐ol which was derived from dodecane‐1,12‐diol, yielding diastereomeric esters mixture. These racemic esters were easily separated by HPLC on silica‐gel. The absolute configurations of the first‐eluted diastereomeric esters from the separated esters were determined using ¹H NMR anisotropy method. Analysis on ¹H NMR spectra and HPLC elution time of the synthesized esters and those of MαNP ester derived from natural methyl‐12‐hydroxystealate showed that the absolute configuration of natural 12‐hydroxystearic acid was R form, and the enantiomeric excess was over 99%.     

Growth of High-Quality Pb((Zn1/3Nb2/3)0.91Ti0.09)O3 Single Crystals by Excess ZnO Addition

A high-quality single crystal of Pb((Zn_1/3Nb_2/3)_0.91Ti_0.09)O₃ (PZNT 91/9), 40 mm in diameter and 20 mm in length, was successfully grown using the solution Bridgman method with a slight excess amount of ZnO. High-quality wafers were sliced from the light-brown single crystal. No PbO inclusions or opaque areas were observed in the transparent wafers. An array probe for echocardiography was constructed with the single-crystal wafer, and its superior performance was demonstrated.     

Study of the Antioxidative Properties of Several Amino Acid-Type Surfactants and their Synergistic Effect in Mixed Micelle

Cysteine and methionine, two sulfur-containing amino acids (AA), were introduced in their surfactant forms as potential antioxidants. The antioxidative (AOX) properties of lauroyl methionine (C12-Met) and lauroyl cysteine (C12-Cys) was investigated by means of the oxygen radical absorbance capacity assay. Both the surfactants exhibited excellent AOX behavior at the premicellar state and micellar medium. The AOX behavior was found to be comparable for both the surfactants at their premicellar states. However, in micellar medium, C12-Met showed better AOX property than C12-Cys. The AOX power of the surfactants was compared with other previously developed AA-type surfactants. The order of the AOX power was found to be: C12-tryptophan > C12-tyrosine ≈ C12-methionine ≈ C12-cysteine > C12-histidine at the premicellar state and C12-tryptophan > C12-tyrosine > C12-methionine > C12-cysteine > C12-histidine at the micellar state. C12-Cys displayed lower AOX property in micellar medium due to its dimer formation tendency. Based on the HPLC and UPLC-Q-TOF-MS analysis, the dimer formation of C12-Cys was found to be accelerated due to the micellar environment and results into negative synergistic effect on other aromatic AA-type surfactants. However, the presence of C12-His in the micellar solution of C12-Cys resulted no synergistic effect due to stronger H-bonding between the surfactants and resulting less dimer formation.     

Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes

Electron-rich, side chain alkynes of an aromatic polyamine were functionalized by a [2+2] cycloaddition, followed by retro-cyclization with the electron-accepting 7,7,8,8-tetracyanoquinodimethane (TCNQ). ¹H NMR studies were used to optimize the reaction conditions. Mild heating to >50?°C afforded the postfunctionalized aromatic polyamines with the desired acceptor amounts. The quantitative TCNQ addition was demonstrated by the MALDI-TOF mass spectrum and elemental analysis. Introduction of the cyano-based acceptor moieties into the polymer side chains resulted in unusually strong intermolecular interactions. In addition to the ?ШC?? interactions of the extended acceptor moieties, these intermolecular forces were supposed to improve the thermal stability of the aromatic polymers. Furthermore, the donor?Cacceptor chromophores formed by this postfunctionalization displayed low energy charge-transfer bands and redox activities in both the anodic and cathodic directions. The straightforward postfunctionalization technique using the alkyne?CTCNQ addition is useful for the preparation of narrow band gap polymers in one step.     

Sintering of the Mechanochemically Activated Powders of Hexagonal Boron Nitride

Pressureless sintering of hexagonal boron nitride (BN) was performed using a powder activated by mechano-chemical treatments. Physical properties of the sintered BN bodies depend on the type of starting powder and the conditions of the treatments. The BN body, which was obtained at 2000°C using an appropriate activated powder, was 99 wt% pure and was excellent in mechanical and physical properties, in spite of its low density (1.64 g/cm³).     

Photochromic nanocomposite films of mononitrosyl complexes embedded in polymer matrices

New photochromic nanocomposite films based on mononitrosyl ruthenium complex [RuCl(NO)py₄]²⁺ have been synthesized by dispersion in polymer matrices. Infrared study under irradiation reveals that the composites present very high population of metastable state (≈45%). Nanoparticles of molecular complex stabilized in different matrices have been observed by transmission electron microscopy.     

Microfabrication of U-Shaped Grooves on the Surface of BaO–TiO2–GeO2 Glass by YAG Laser Irradiation and Selective Chemical Etching

A combination technique of Nd:YAG laser (wavelength: 1064 nm) irradiations and chemical etchings was applied to fabricate microsize U-shaped grooves on the surface of CuO-doped BaO–TiO₂–GeO₂ glass, and chemical etching behaviors were examined by using a confocal scanning laser microscope. Continuous-wave Nd:YAG lasers with a power of 0.7–0.8 W were irradiated onto the glass surface and scanned at a speed of 10 μm/s, inducing structural modified lines with refractive index changes. The chemical etching rates for the refractive index changed lines in a nitric acid solution (1 N HNO₃) were larger than those for the base glass (nonirradiated part). The etching profile was changed gradually from W-shaped to U-shaped grooves with increasing etching time. The sharp bending lines with an angle of 150° and the cross-linked lines were also smoothly etched. The U-shaped grooves with a surface covered by nonlinear optical Ba₂TiGe₂O₈ crystals were formed by the crystallization of etched samples. This study proposes that the patterning of microchannels with optical functional surfaces is possible on the glass surface using the present technique.