Direct determination of benzamides in serum by column-switching high-performance liquid chromatography.

A column-switching high-performance liquid chromatographic method with fluorescence detection was developed for the simultaneous determination of four benzamide-type anti-psychotic drugs: sulpiride, tiapride, sultopride and metoclopramide in human serum. In this method, a TSKgel Super-ODS column was used as an analytical column, and a TSKgel G 2000SW was prepared as a pretreatment column. Under the optimized analytical conditions, four benzamide-type anti-psychotic drugs were eluted within 18 min. The detection limits (S/N = 3) for sulpiride, tiapride, sultopride and metoclopramide are 1 ng/ml, 4 ng/ml, 2 ng/ml and 0.5 ng/ml, respectively. Finally, the method was applied to the determination of sulpiride in human serum samples obtained after a single oral dose of sulpiride.     

Synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine and (±)-convolutamydines A and E, through enolization-Claisen rearrangement of 2-allyloxyindolin-3-ones

Claisen rearrangement triggered by enolization of 2-allyloxyindolin-3-ones with DBU was performed in order to prepare 3-allyl-3-hydroxyindolin-2-ones. Total synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine, as well as (±)-convolutamydines A and E, was achieved by transformation of the allyl moiety of 3-allyl-3-hydroxyindolin-2-ones.     

Analysis of dielectric relaxations of w/o emulsions in the light of theories of interfacial polarization

An attempt is made to apply dielectric theories of interfacial polarization to observations of dielectric relaxations for W/O emulsions. Approximate formulas for disperse systems in a W/O type were derived from the two theories: one proposed by Maxwell and Wagner for dilute disperse systems of spherical particles, and the other developed by Hanai for concentrated disperse systems. Dielectric measurements were carried out on concentrated W/O emulsions prepared from kerosene and distilled water or KCl aqueous solutions by minimal use of emulsifiers. Marked dielectric relaxations were observed with the emulsions, the dielectric parameters having been determined to characterize the relaxation data. Phase parameters such as relative permittivity, electric conductivity and volume fraction of the disperse phase were evaluated from the dielectric parameters by use of the approximate formulas of the respective theories. The phase parameters evaluated and the frequency dependence of complex permittivity of the W/O emulsions deduced from the theory for concentrated disperse systems are in excellent agreement with the observed data in comparison to that for dilute disperse systems. It is concluded that the dielectric relaxations due to the interfacial polarization of disperse systems of spheres are explained satisfactorily by the theory for concentrated disperse systems.     

Rapid ruthenium-catalyzed synthesis of pyranopyrandiones by reconstructive carbonylation of cyclopropenones involving C[bond]C bond cleavage

Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions.     

New class of potent catalysts of O2.-dismutation. Mn(III) ortho-methoxyethylpyridyl- and di-ortho-methoxyethylimidazolylporphyrins

Three new Mn(III) porphyrin catalysts of O2.-dismutation (superoxide dismutase mimics), bearing ether oxygen atoms within their side chains, were synthesized and characterized: Mn(III) 5,10,15,20-tetrakis[N-(2-methoxyethyl)pyridinium-2-yl]porphyrin (MnTMOE-2-PyP(5+)), Mn(III)5,10,15,20-tetrakis[N-methyl-N'-(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTM,MOE-2-ImP(5+)) and Mn(III) 5,10,15,20-tetrakis[N,N'-di(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTDMOE-2-ImP(5+)). Their catalytic rate constants for O2.-dismutation (disproportionation) and the related metal-centered redox potentials vs. NHE are: log k(cat)= 8.04 (E(1/2)=+251 mV) for MnTMOE-2-PyP(5+), log k(cat)= 7.98 (E(1/2)=+356 mV) for MnTM,MOE-2-ImP(5+) and log k(cat)= 7.59 (E(1/2)=+365 mV) for MnTDMOE-2-ImP(5+). The new porphyrins were compared to the previously described SOD mimics Mn(III) 5,10,15,20-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP(5+)), Mn(III) 5,10,15,20-tetrakis(N-n-butylpyridinium-2-yl)porphyrin (MnTnBu-2-PyP(5+)) and Mn(III) 5,10,15,20-tetrakis(N,N'-diethylimidazolium-2-yl)porphyrin (MnTDE-2-ImP(5+)). MnTMOE-2-PyP(5+) has side chains of the same length and the same E(1/2), as MnTnBu-2-PyP(5+)(k(cat)= 7.25, E(1/2)=+ 254 mV), yet it is 6-fold more potent a catalyst of O2.-dismutation , presumably due to the presence of the ether oxygen. The log k(cat)vs. E(1/2) relationship for all Mn porphyrin-based SOD mimics thus far studied is discussed. None of the new compounds were toxic to Escherichia coli in the concentration range studied (up to 30 microM), and protected SOD-deficient E. coli in a concentration-dependent manner. At 3 microM levels, the MnTDMOE-2-ImP(5+), bearing an oxygen atom within each of the eight side chains, was the most effective and offered much higher protection than MnTE-2-PyP(5+), while MnTDE-2-ImP(5+) was of very low efficacy.     

Theoretical approach and the practice to the evaluation of structural parameters characterizing concentration polarization alongside ion-exchange membranes by means of dielectric measurement

As the application of a dielectric theory proposed previously (J Membrane Sci 64:153–161 (1991)), theoretical formulation and the practical procedure of dielectric analysis are developed to calculate the structural parameters such as the conductivity gradient and the thickness of the concentration polarization layer, the capacitances and the conductances of the two adjoining aqueous phases from the observed dielectric parameters. The procedure of calculation consequent upon the theoretical formulation was applied to double relaxation data observed for cation-exchange membrane systems under application of d.c. bias voltage. As a consequence, the structural parameters of concentration polarization were readily obtained with accuracy.     

Analysis of the mechanism of retention on graphitic carbon by a computational chemical method

Retention mechanism on a graphitic carbon was analyzed by computational chemical calculation. The model graphitic carbon phase was a large polycyclic aromatic hydrocarbon (PAH) and analytes were carbohydrates and hydrocarbons separated by liquid and gas chromatography. Molecular mechanics calculation was fast and suggested their retention order and main retention force. Molecular orbital package calculation (MOPAC) demonstrated their complex form.     

Wavelength effect on the photoinduced reaction of polymethylmethacrylate

Polymethylmethacrylate (PMMA) containing benzophenone (BP) was photo-irradiated with monochromatic radiation of wavelength 260–360 nm using the Okazaki Large Spec-trograph (OLS). On irradiation of PMMA films containing BP in air, the sensitized main-chain scission and photocrosslinking of PMMA took place simultaneously. These reactions are dependent on irradiation wavelength. The threshold wavelength for both reactions is found to be ca. 380 nm. The number of main-chain scission and amount of gel increased with the increase of BP concentration in PMMA. Photosensitized main-chain scission favors the irradiation of radiation at ca. 280 nm and photocrosslinking takes place efficiently with the exposure of 340 nm radiation. A possible mechanism for photosensitized reaction is proposed. © 1995 John Wiley & Sons, Inc.