Determination of triazine pesticides and related compounds in environmental water by liquid chromatography-mass spectrometry.

A method for the determination of 5 triazine herbicides and 12 degradation products in environmental water samples using liquid chromatography-electrospray ionization mass spectrometry (LC/ESI/MS) has been developed. The pesticides in water were extracted with two types of solid phase: a styrene-divinylbenzene copolymer and a graphitized carbon black. Desorption solvents for the extracted compounds were acetone for the styrene-divinylbenzene copolymer and methanol for the graphitized carbon black. Overall recoveries from ground water and river water ranged from 73% to 111%. The limits of detection (LODs) were 0.2 to 28 ng l(-1). This method was applied to several ground water samples.     

Total synthesis of tylosin

Tylosin has been synthesized byregio- and stereoselective introduction of the amino disaccharide moiety and D-mycinose onto the previously synthesized 16-membered-ring aglycone.     

Excited states of porphyrin isomers and porphycene derivatives: a SAC-CI study

Excited states of free-base porphyrin isomers, porphycene (Pc), corrphycene (Cor), and hemiporphycene (hPc), were studied by the Symmetry-Adapted Cluster (SAC)/SAC-Configuration Interaction (CI) method. The absorption peaks of the porphyrin isomers were assigned on the basis of the SAC-CI spectra. The X, Y, X', and Y' bands of the porphyrin isomers, which have weak intensities, are identified. The differences in the Q-band absorptions among the isomers were clearly explained by the four-orbital model. In Cor and hPc, the wave function of the B-band corresponds to the mixture of the four-orbital excitations and the optically forbidden excitation of free-base porphin (P), due to the molecular symmetry lowering in the isomers. The B-band character is described by the five-orbital model in Pc and the six-orbital model in Cor and hPc. Two tetrazaporphycenes and two ring-extended (dibenzo) porphycenes were designed, and the Q-band transition moment was successfully controlled. These examples show that the control of the four-orbital energy levels is the guiding principle for pigment design in porphyrin compounds.     

Spirostane derivatives highly oxygenated at A and B rings from the rhizomes of rohdeajaponica roth and of campylandra aurantiaca baker

Two steroidal compounds BR-1 (I) and ?2 (II) which had been obtained from the rhizomes of $\text{Campylandra aurantiaca}$ Baker, were isolated also from those of $\text{Rohdea japonica}$ Roth. They were identified, respectively, by X-ray analysis and chemical correlation as 1β,2β,3β,4β,5β,7α-hydroxy-spirost-25(27)-en-6-one and its corresponding 6β-hydroxy compound.     

The first example of the stereoselective synthesis of 7 beta-carbamoyl-4,5alpha-epoxymorphinan via a novel and reactive gamma-lactone

7beta-Carbamoyl-4,5alpha-epoxymorphinans 5 were stereoselectively synthesized from the 7alpha-carboxylate intermediate 3 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and amines under reflux conditions in mesitylene via a novel and reactive gamma-lactone 7. These were the first examples of the stereoselective syntheses of 7beta-substituted 4,5alpha-epoxymorphinans. The mechanism of the reaction process was elucidated as follows: 1) epimerization of 7alpha-carboxylate 3, 2) intramolecular lactonization of 7beta-carboxylate 6, and 3) aminolysis of the resultant gamma-lactone 7. The aminolysis of the isolated reactive gamma-lactone 7 with allylamine and the alcoholysis with MeOH in the presence of NaBH(4) proceeded at room temperature. The gamma-lactone 7 can be a useful intermediate for the preparation of 7beta-substituted 4,5alpha-epoxymorphinans that would be potent selective delta opioid receptor ligands. The stereoselective syntheses of the 7alpha-carbamoyl-4,5alpha-epoxymorphinans 9 from 7alpha-carboxylate 3 via 7alpha-carboxylic acid were also successful.     

Optically active 1,2-bis(1-arylhydroxymethyl) ferrocene: a new, efficient chiral ligand for scandium-catalyzed asymmetric Diels-Alder reaction

[reaction: see text] The Sc(OTf)3/FERRODIOL (2) complex was prepared at -78 degrees C in CH2Cl2 in the presence of 2,6-lutidine and MS 4A. The chiral scandium Lewis acid-catalyzed asymmetric Diels-Alder reaction of cyclopentadiene (3) with 3-acyloxazolidin-2-ones (4) effectively produced the adduct (5) in a high yield with good selectivity, i.e., endo/exo = 90:10 up to 91% ee (endo).     

Dynamics of order formation by colloidal adsorption onto a substrate studied with Brownian dynamics

Colloidal adsorption and spontaneous ordering of adsorbed particles on a substrate was simulated using a three-dimensional simulation model for colloidal dispersion system with an adsorptive surface under a specified bulk concentration, where the particle-particle and particle-substrate interactions were modeled on the DLVO theory. The key process for order formation is considered to be the adsorption of a particle that induces the transition from incomplete order to perfect order, and is found to involve a stochastic nature due to an energy barrier which must be overcome for the system to reach ordered state. Also, a model was developed to predict the energy barrier for order formation based on direct observation of the key process. Further, a model to describe the stochastic nature of the process was developed and its quantitative validity was demonstrated. Through the examination of the key process, it is concluded that the mechanism of the order formation is composed of two successive processes and the rate-determining step varies depending on the ionic strength.     

Ultramicrodetermination of nitrogen in organic compounds: VI. Capillary immutability due to glass corrosion by various solutions

The capillary immutability due to corrosion of glasses exposed to various solutions was studied. The analytical error of volume change caused by glass corrosion in a micro- and ultramicronitrometer was discussed. The present work has shown that the graduated tube of a decimicronitrometer made of borosilicate glass, which is used frequently in Dumas method, should be recalibrated after 1.5–2.3 months use. We therefore recommend the sealed tube method using an improved nitrometer for ultramicrodetermination of nitrogen in organic compounds.