Purification of a marine bacterial glucose dehydrogenase fromCytophaga marinoflava and its application for measurement of 1,5-anhydro-d-glucitol

A novel glucose dehydrogenase (GDH) from a marine bacteriumCytophaga marinoflava IFO 14170 was isolated from its membrane fraction. This GDH catalyzes the oxidation of a hydroxy group of glucose, but does not react in its C-l position. This enzyme is composed of a single peptide with a mol wt of 67,000. The GDH can react under high salinity. The optimum pH is around 8.0, showing a typical property of marine bacterial enzymes. Using this novel enzyme, an enzymatic determination of 1,5-anhydro-D-glucitol (1,5AG) utilizing 2,6-dichrolophenolindophenol (DCIP) and phenazine methosulfate (PMS) as electron mediators was caried out. A good linear correlation was observed from 0.5 mM to 4 mM of 1,5AG.     

Separation and determination of some stereoisomers by capillary gel electrophoresis with cyclodextrin incorporated in polyacrylamide gel

Capillary gel electrophoresis (CGE) was successfully applied to the separation of optically active isomers and position isomers by incorporating a suitable cyclodextrin chiral selector in polyacrylamide gel. A commercially available ß-cyclodextrin (ß-CD) was used for enantioselectivity towards o-, m- and p-nitrobenzoic acid, o-, m- and p-hydroxybenzoic acid, o-, m- and p-toluic acid and the optical isomers of dansyl-D,L-leucine and R,S-1,1-binaphthyl-2,2-dihydrogenphosphate. Especially the effect of organic solvents, such as acetonitrile, methanol, dimethylsulphoxide and others were examined in detail. The resolution varied to some extent with the addition of the organic solvent to the polyacrylamide gel and the running buffer solution. The possible mechanism has also been discussed. In addition, quantitative aspects of the separation of stereoisomers using CGE have been studied, showing that both the resolution and accuracy of the determinations were affected by the ratio of the enantiomers.     

One-pot preparation of chiral beta-amino esters by rhodium-catalyzed three-components coupling reaction

Chiral beta-amino esters are synthesized in one-pot from three components, amines, aldehydes, and ethyl bromoacetate, under the rhodium-catalyzed Reformatsky-type reaction condition, where complete diastereoselection is achieved in the nucleophilic addition step of ethyl bromoacetate to the imines prepared in     

Dissociation equilibrium between uncharged and charged local anesthetic lidocaine in a surface-adsorbed film

The dissociation equilibrium between uncharged local anesthetic lidocaine (LC) and charged local anesthetic LC (LCH⁺) in a surface-adsorbed film was investigated by measuring the surface tension and pH of aqueous solutions of a mixture of hydrochloric acid and LC. The surface tension values decreased slightly with increasing total molality m_t at 0X₂0.5, where X₂ is the mole fraction of LC in the mixture, while they decreased rapidly with increasing m_t at 0.5<X₂1. It was shown from the pH measurements that almost all LC molecules were changed into LCH⁺ ions by protonation at 0X₂0.5 and both forms coexisted only at 0.5<X₂1. The quantities of the respective LC and LCH⁺ transferred from the aqueous solution to the adsorbed film, i.e., their surface densities, were calculated by applying the thermodynamic equations derived to the surface tension and pH data. A greater quantity of LC than LCH⁺ existed in the adsorbed film at the coexisting composition. The partitioning behavior of LC and LCH⁺ in the adsorbed film was characterized by three composition regions: (1) slight partitioning of low surface-active LCH⁺ in the region at 0X₂0.5, (2) preferential partitioning of LC at 0.5<X₂<around 0.7, and (3) negative partitioning of LCH⁺ at around 0.7X₂1. The present results clearly indicate that uncharged local anesthetics transfer into hydrophobic environments such as cell membranes more than charged ones.     

Concise synthesis of pyrrolophenanthridine alkaloids using a Pd-mediated biaryl coupling reaction with regioselective C-H activation via the intramolecular coordination of the amine to Pd

The concise synthesis of Amaryllidaceae alkaloids, such as anhydrolycorinone, anhydrolycorin-7-one, assoanine, and oxoassoanine, which have a pyrrolophenanthridine skeleton, was achieved in moderate yield using the Pd-mediated biaryl coupling reaction of 1-(2-halobenzyl)-2,3-dihydroindole, which applied the regioselective C-H activation method with intramolecular coordination of the benzylamino group to Pd.     

Photoluminescence enhancement of PEG-modified YAG:Ce3+ nanocrystal phosphor prepared by glycothermal method

Y3Al5O12:Ce3+ (YAG:Ce3+) nanocrystals were synthesized in 1,4-butylene glycol (BG) with and without poly(ethylene glycol) (PEG) by the glycothermal method. The internal quantum efficiency of the photoluminescence (PL) corresponding to the 5d --> 4f transition of Ce3+ in the YAG:Ce3+ nanocrystal increased from 21.3 to 37.9% by addition of PEG, while no appreciable change in the primary particle size, the crystallite size, and the lattice distortion was recognized by transmission electron microscopy and X-ray diffractometry. The thermogravimetry-differential thermal analysis, Fourier transform infrared absorption spectroscopy and 1H --> 13C cross-polarization magic angle spinning nuclear magnetic resonance (CP-MAS NMR) confirmed the preferential coordination of PEG to the YAG:Ce3+ nanocrystal. 27Al single-pulse excitation MAS NMR reveals that the ratio of the 4-fold coordination site to the 6-fold coordination site increased from 0.53 to 0.72 by addition of PEG. We conclude that the surface modification of the YAG:Ce3+ nanocrystal by PEG induces the surface passivation, the prevention of the oxidation of Ce3+ to Ce4+, the promotion of the incorporation of Ce3+ into YAG and the local structural rearrangement, resulting in the PL enhancement.     

5-Fluorouracil derivatives with serum protein binding potencies

To develop an optimal delivery system for 5-fluorouracil (5FU) using serum protein as a drug carrier, a series of its benzyl derivatives was synthesized. Then their binding to the serum protein was investigated by equilibrium dialysis. The benzyl derivatives of 5FU were strongly bound to rat plasma protein or human serum albumin. The bound percentage increased with increasing hydrophobicity. It was suggested that the benzyl derivative of 5FU existed in the blood as a complex with serum albumin and circulated for a long time as a polymeric drug does.