Electrophoretic mobility of the polymer-like micelles of tetradecyldimethylamine oxide hemihydrochloride

Effects of the surfactant concentration C_d and the NaCl concentration C_s on the electrophoretic mobilities U of the well-characterized polymer-like micelles have been investigated by the electrophoretic light scattering, using tetradecyldimethylamine oxide hemihydrochloride (C14DMAO·1/2HCl). At the high ionic strength of 0.1 mol kg⁻¹ NaCl, the electrophoretic mobilities were independent of C_d (5 mM < C_d < 100 mM), despite the concentration-dependent micelle growth of the polymer-like micelles. This suggests that the electrophoretic mobility of the polymer-like micelle at high ionic strengths is independent of the contour length (i.e., the molecular weight), as found on linear polyelectrolytes. Somewhat surprisingly, the entanglements of the polymer-like micelles gave small effect on the electrophoretic mobilities in the examined range of the surfactant concentration above an overlap concentration. The mobilities of the polymer-like micelle decreased with √C_s in a single exponential manner in the range of C_s from 0.02 to 0.3 mol kg⁻¹. It is suggested that the cylinder model can be applied to the electrophoretic mobilities of the polymer-like micelles at high ionic strengths (i.e. a free-draining behavior), since the persistence length of the polymer-like micelle (20 nm) is much larger than the Debye length at high ionic strength.     

Groove-spanning behavior of lipid membranes on microfabricated silicon substrates

We report on a spreading behavior of phospholipid membranes that arise from a lump of phospholipid (a lipid source) on topographically patterned substrates immersed in an aqueous solution. Microgrooves with well-defined shapes were prepared on Si111 surfaces by anisotropic etching in an alkaline solution. A spreading front that consists of membrane lobes and a single lipid bilayer was observed on the patterned silicon substrates by utilizing fluorescence interference contrast (FLIC) microscopy. FLIC images indicate that the membrane lobes span the microgrooves, while the underlying single lipid bilayer spread along the surface of the microgrooves. In fact, fluorescent polystyrene nanoparticles could be encapsulated in the microgrooves that were completely covered with the membrane lobes. The groove-spanning behavior of membrane lobes is discussed in terms of a balance between adhesion and bending energies of lipid bilayers.     

Ion-exclusion chromatography with conductimetric detection of aliphatic carboxylic acids on a weakly acidic cation-exchange resin by elution with benzoic acid-beta-cyclodextrin

In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression.     

Preparation and characterization of modified 3-aminopropylsilyl silica phases with 1,8-naphthalic anhydrides in HPLC

Modified 3-aminopropylsilyl silica stationary phases with 1,8-naphthalic anhydrides [3-(1,8-naphthalimido)propyl (NAIP), 3-(4-amino-1,8-naphthalimido)propyl (4A-NAIP), 3-(3-nitro-1,8-naphthalimido)propyl (3N-NAIP), and 3-(4-nitro-1,8-naphthalimido)propyl modified silyl silica gel (4N-NAIP)] are prepared in a single reaction. Chromatographic properties of these phases are characterized using various solutes including monosubstituted benzenes, alkyl benzenes, and polycyclic aromatic hydrocarbons (PAHs) in high-performance liquid chromatography. Even though the retention in these NAIPs is mainly based on the reversed-phase mode, 3N- and 4N-NAIP show a remarkable recognition toward aromatic hydrocarbons, which is attributed to their strong pi-pi interaction. Furthermore, the recognition ability is according to the molecular planarity and non-linearity of PAHs. Subsequently, 3N- and 4N-NAIP has a distinct selectivity from octadecyl silica and, therefore, will be a valuable alternative for a separation or a solid-phase extraction of aromatic compounds.     

Enantioselective reduction of ketones with optically active 2,2′-diamino-6,6′-dimethylbiphenyl-lithium aluminum hydride complex

Enantioselective reductions of prociral ketones with chiral hydride reagent prepared from optically active 2,2′-diamino-6,6′-dimethylbiphenyl and lithium aluminum hydride were accomplished in O.Y. more than 50%.     

Mass spectra of π-cyclopentadienyl-diene cobalt complexes

Many reports on the mass spectra of organotransition-metal complexes have appeared in recent years,¹ whilst there have only been a few reports on the mass spectra of transition metal olefin complexes, some metal carbonyl olefin complexes²³⁴ and π-cyclooctenyl-π-cyclooctadienyl cobalt.⁵ Recently fragmentation paths of π-cyclopentadienyl-cyclooctadiene rhodium were elucidated by King.⁶ The present authors found metastable ions in the mass spectra of π-cyclopentadienyl-diene cobalt complexes as well as in the mass spectra of π-cyclopentadienyl-diene rhodium complexes.⁷. In the present paper the authors wish to report the mass spectra of several π-cyclopentadienyl diene cobalt complexes.     

Designer ribozymes: programming the tRNA specificity into flexizyme

Fx3 is an artificial ribozyme with the ability to aminoacylate various tRNAs with phenylalanine and its nonnatural derivatives. Herein we report a simple strategy to build tRNA specificity into the generic Fx3, by appending to its 3'-end a tRNA-specific sequence (TSS), which is complementary to the acceptor stem of the cognate tRNA. This new designer ribozyme, referred to as Fx10, is able to recognize its cognate tRNA via a 10-base-pair interaction that is formed after the invasion of the tRNA acceptor stem by the TSS. We have demonstrated that Fx10 can aminoacylate its cognate tRNA with a high degree of specificity and also discriminate against the noncognate tRNAs. Because the tRNA specificity can be easily programmed into Fx10, it is a custom-made catalyst to generate nonnatural aminoacyl-tRNAs.     

Solvothermal synthesis of large surface area zirconia

The reaction of zirconium n-propoxide in glycol at 300°C yielded microcrystalline tetragonal zirconia (ZrO₂). The crystallite size of the product depended on the carbon number of the glycol and increased in the following order (carbon number of glycol): 2<6<4, which suggested that the heterolytic cleavage of O-C bond of gylcoxide formed by transesterification is the prime factor for the formation of the product. In toluene, zirconium isopropoxide also gave tetragonal zirconia at 300°C, and zirconium tert-butoxide decomposed at 200°C yielding amorphous zirconia, while zirconium n-propoxide was stable at 300°C. These results suggest that the reaction in toluene depends on the structure of the alkyl group of the alkoxides. Thus-obtained tetragonal zirconias maintained large surface areas (90–160 m²/g) even after calcination at 500°C.