Circularly polarized luminescence of rhodamine B in a supramolecular chiral medium formed by a vortex flow

Sucked into the vortex: Hydrogels with embedded Rhodamine?B dye showed stir-induced circularly polarized luminescence (CPL; see picture), the sense of which can be controlled by switching the stir direction from clockwise (CW) to counterclockwise (CCW) with slow cooling from the sol to gel states. The chiral alignment of the dye was erased by heating the sample above the gel-sol transition temperature.     

Two-dimensional residual charge density distribution measurement of surface leader

The charge density distribution of the surface leader has never been measured before. Because the surface leader usually covers a long distance, and the surface potential caused by leader discharge is usually very high, this creates difficulties in measuring the potential distribution of the surface leader. In this paper, with a feedback type electrostatic probe based on a field-nullify technique, a charge density distribution scanning system is developed. A two-layer structure pipe is designed to lower the surface potential after discharge. In this way, the surface potential distribution caused by the residual charge of the leader discharge under the application voltage as high as to 40 kV can be measured. The surface charge density distribution including the leader and streamer is perfectly measured, which is in good agreement with the photograph.     

Reproduction of a protocell by replication of a minority molecule in a catalytic reaction network

For understanding the origin of life, it is essential to explain the development of a compartmentalized structure, which undergoes growth and division, from a set of chemical reactions. In this study, a hypercycle with two chemicals that mutually catalyze each other is considered in order to show that the reproduction of a protocell with a growth-division process naturally occurs when the replication speed of one chemical is considerably slower than that of the other chemical, and molecules are crowded as a result of replication. It is observed that the protocell divides after a minority molecule is replicated at a slow synthesis rate, and thus, a synchrony between the reproduction of a cell and molecule replication is achieved. The robustness of such protocells against the invasion of parasitic molecules is also demonstrated.     

GD3- and O-acetylated GD3-gangliosides in the GM2 synthase-deficient mouse brain and their immunohistochemical localization

Gangliosides in the brain of the knockout mouse deficient in the activity of β1,4 N-acetylgalactosaminyl transferase (β1,4 GalNAc-T)(GM2 synthase) consisted of nearly exclusively of GM3- and GD3-gangliosides as expected from the known substrate specificity of the enzyme and in confirmation of the initial reports from two laboratories that generated the mutant mouse experimentally. The total molar amount of gangliosides was approximately 30% higher in the mutant mouse brain than that in the wild-type brain. However, contrary to the initial reports, one-fourth of total GD3-ganglioside was O-acetylated. It reacted positively with an anti-O-acetylated GD3 monoclonal antibody and disappeared with a corresponding increase in GD3-ganglioside after mild alkaline treatment. The absence of O-acetylated GD3 in the initial reports can be explained by the saponification step included in their analytical procedures. Although quantitatively much less and identification tentative, we also detected GT3 and O-acetylated GT3. Anti-GD3 and anti-O-acetylated GD3 monoclonal antibodies gave positive reactions in the brain of mutant mouse as expected from the analytical results. Either antibody barely stained wild-type brain except for immunoreactivity of GD3 in the cerebellar Purkinje cells. The distributions of GD3 and O-acetylated GD3 in the brain of mutant mouse were similar but differential localization was noted in the cerebellar Purkinje cells and cerebral cortex.     

Novel Ti-O-Ti bonding species constructed in a metal-oxide cluster

The preparation and structural characterization of a novel Ti-O-Ti bonding complex constructed in the mono-lacunary alpha-Keggin polyoxometalate (POM), are described. The water-soluble, crystalline complex with a formula of K5H2[[{Ti(OH)(ox)}2(micro-O)](alpha-PW11O39)] x 13H2O 1 was prepared in 30.2% (0.60 g scale) yield in a 1 : 3 molar-ratio reaction of the tri-lacunary species of alpha-Keggin POM, Na9[A-PW9O34] x 19H2O, with the titanium(IV) source, K2TiO(ox)2 x 2H2O (H2ox = oxalic acid), in HCl-acidic solution (pH 0.08), and characterized by complete elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), FTIR, solution (31P, 183W, 1H and 13C) NMR spectroscopy and X-ray crystallography. The complex was also obtained in 47.6% (0.81 g scale) yield in a 1 : 2 molar-ratio reaction of the mono-lacunary Keggin POM, K7[PW11O39] x 10H2O, with the anionic titanium(IV) complex under acidic conditions. The molecular structure of [[{Ti(OH)(ox)}2(micro-O)](alpha-PW11O39)]7- 1a, was successfully determined. This POM in the solid state is composed of one host (mono-lacunary site) and two guests (two octahedral Ti groups), in contrast to most titanium (IV)-substituted POMs consisting of one host and one guest. On the other hand, the 31P NMR measurements revealed that in aqueous solution this POM was present under a dissociation equilibrium which depends upon both temperature and pH.     

A novel chip device based on wired capillary packed with high performance polymer-based monolith for HPLC: reproducibility in preparation processes to obtain long columns.

This report describes the development of novel wired chip devices for mu-HPLC analyses. The monolithic capillary column to be wired was prepared using a tri-functional epoxy monomer, tris(2,3-epoxypropyl)isocyanurate with a diamine, 4-[(4-aminocyclohexyl)methyl]cyclohexylamine. The prepared column was evaluated by SEM observation of the sectional structure of column and micro-HPLC. In addition, the reproducibility in the preparation of long capillary columns having nearly 1 m length was extensively examined for applications of novel wired chip devices. The authors demonstrated that the monolithic structure of the prepared long capillary could be finely controlled under the strictly maintained operational conditions and thus the relative standard deviation (RSD) of the column properties such as the number of theoretical plates, retention factor, and permeability could be well controlled to become less than 10%. Furthermore, the wired chip device column showed that its high performance was kept even after chip preparation.     

Synthesis of panax acetylenes: chiral syntheses of acetylpanaxydol, PQ-3 and panaxydiol

Acetylpanaxydol (1-Ac), PQ-3 (2) and panaxydiol (3) and their optical isomers were synthesized from L-(+)-diethyl tartrate. The absolute configurations of 1-Ac, 2 and 3 were determined to be 1-Ac (3R,9R,10S), 2 (9R,10S) and 3 (3R,10S), respectively, by comparisons of their optical rotations and the NMR data of their MTPA esters with those of natural products.     

Organocatalytic direct asymmetric aldol reactions in water

We have developed direct asymmetric cross-aldol reactions that can be performed in water without addition of organic solvents. A bifunctional catalyst with a long hydrophobic alkyl chain efficiently catalyzed the reactions and afforded the desired aldol products in excellent yield with high enantiomeric excess, even when only an equal molar ratio of the donor and acceptor was used. These results reveal an effective design strategy for the development of aqueous organocatalytic systems.