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.     

Non-existence of phase transition of oriented percolation on Sierpinski carpet lattices

 A percolation problem on Sierpinski carpet lattices is considered. It is obtained that the critical probability of oriented percolation is equal to 1. In contrast it was already shown that the critical probability p _c of percolation is strictly less than 1 in Kumagai [9]. This result shows a difference between fractal-like lattice and ℤ ^d lattice. Received: 15 May 2002 / Revised version: 11 October 2002 / Published online: 21 February 2003 Mathematics Subject Classification (2000): Primary: 60K35, 82B43; Secondary: 82B26     

Lightness Change as Perceived in Relation to the Size of Recognized Visual Space of Illumination

According to the concept of the recognized visual space of illumination (RVSI) the lightness of an object surface is perceived in relation to its conceptualized size. To prove this proposition the lightness of gray test patches was judged when they were located at various positions inside an illuminated space composed of two rooms in the depth direction from a subject. No retinal image arrangement was changed in the test patch and its immediate surroundings, but the front room had walls, floors and furniture lower in lightness by the amount of N1.5 than the back room to make the RVSI of the former smaller despite the illuminance in the entire space being the same. The results showed that the apparent lightness of the patches was perceived higher by amount of about 13 in L units for the N4 test patch and about 20 for N6 when the patches were located in the front room, in accordance with the prediction. It was stressed that the experiment of lightness judgment should be conducted in a three dimensional space rather than two dimensional plane as done by several investigators.     

A conducting crystal based on a single-component paramagnetic molecule, [Cu(dmdt)(2)] (dmdt = dimethyltetrathiafulvalenedithiolate)

A single-component conducting molecular crystal composed of paramagnetic copper complexes, [Cu(dmdt)2]0+, was prepared. The crystal has an unprecedented three-dimensionally packed molecular arrangement and exhibits a fairly high conductivity (1 S cm-1 at room temperature). The magnetic susceptibility measurements revealed that [Cu(dmdt)2]0+ molecule keeps most of S = 1/2 spin moments. The difference of the bond lengths between [Cu(dmdt)2]0+ and [Cu(dmdt)2]2- is consistent with the result of the molecular orbital calculation.     

Cidep study of radical-ion pair systems: Photooxidation reactions of carbazoles by maleic anhydride in alcohol solution

Photooxidation (charge transfer) reactions of carbazole derivatives by maleic anhydride (MA) in alcoholic media are studied by a time-resolved cw-ESR (TRESR) and Fourier transform ESR (FTESR) techniques. The CIDEP spectra observed in the systems (methyl-, ethyl-, and phenyl-substituted carbazoles with MA) remarkably depend on the MA concentration. Under the high concentration conditions, an emissive TM (triplet mechanism) polarization with a slight A/E (absorption/emission) pattern of the RPM (radical pair mechanism) is observed. In the low concentration of MA, a TM-like absorptive polarization is superimposed on the A/E pattern of the RPM. Since this reaction takes place exclusively through the triplet state, this spectral phase reveals that the singlet state of the radical-ion pair (RIP) has an energy higher than that of the triplet state, in other words, the sign of the apparent exchange interaction of the present RIP systems is positive. The total absorptive polarization observed in the low concentration of MA is tentatively explained by the polarization transfer from the excited triplet state of carbazoles in thermal equilibrium.     

Synthesis and two-electron redox behavior of diazuleno[2,1-a:1,2-c]naphthalenes

The Diels-Alder reaction of di-2-azulenylacetylene with tetraphenylcyclopentadienone afforded 7,8,9,10-tetraphenyldiazuleno[2,1-a:1,2-c]naphthalene in one pot via autoxidation of the presumed 1,2-di-2-azulenylbenzene derivative. In contrast, a similar reaction of bis(1-methoxycarbonyl-2-azulenyl)acetylene with tetraphenylcyclopentadienone gave the 1,2-di-2-azulenylbenzene derivative. The following cyclodehydrogenation reaction of the benzene derivative with iron(III) chloride afforded diazuleno[2,1-a:1,2-c]naphthalene 6,11-bismethoxycarbonyl derivative. The redox behavior of these novel diazuleno[2,1-a:1,2-c]naphthalenes was examined by cyclic voltammetry (CV). These compounds exhibited two-step oxidation waves at +0.22 to +0.71 V upon CV, which revealed the formation of a radical cation and dication stabilized by the fused two azulene rings under the electrochemical oxidation conditions. Since the 1,2-di-2-azulenylbenzene derivative was oxidized at higher oxidation potentials (+0.83 and +1.86 V), the fusion of the two azulene rings to naphthalene increased electron-donating properties because of the formation of a closed-shell dicationic structure. Formation of the radical cation was characterized by UV-vis spectroscopy under the electrochemical oxidation conditions, although no evidence was obtained for the presumed dication under the conditions of the UV-vis spectroscopy measurement.     

Ion-Pair Solvent Extraction of EDTA Anions with Tetraalkylammonium Ions in Various Organic Solvents

Summary.  The ion-pair solvent extraction behavior of ethylenediaminetetraacetate (EDTA) anion by various tetraalkylammonium ions was investigated at 25.0 ± 0.1°C. The extraction of EDTA exceeded 90% from the basic aqueous solution into the organic solvents such as n-hexane and benzene derivatives containing tri-n-octylmethylammonium chloride, but EDTA was hardly extracted from acidic solution. Among the chemical species of EDTA in aqueous solution, edta ⁴⁻ is the most extractable one. On the other hand, the extraction of EDTA was less than 1% into chloroform and 1,2-dichloroethane even from the basic aqueous solution. The effect of the structure of alkylammonium ion was also examined. Tetra-n-hexylammonium and tetra-n-octylammonium ions could not extract EDTA even from the basic aqueous solution, while the use of tri-n-octylmethylammonium and di-n-lauryldimethylammonium ions enhances the extraction of EDTA. These results suggest that the steric hindrance in the ion-pair of alkylammonium and EDTA anion in the organic phase affects the extractability of EDTA containing ion-pair. The solution structure of ion-pair in the organic phase was calculated by MMFF force field and the steric effect in the ion-pair was also suggested. From the extraction constants obtained, the possibility of the extraction separation of EDTA has been shown. Present address: Chemistry Department, Heilongjiang University, Harbin, China     

Synthetic studies of proanthocyanidins. Part 3: Stereoselective 3,4-cis catechin and catechin condensation by TMSOTf-catalyzed intramolecular coupling method

TMSOTf-catalyzed intramolecular condensation for catechin and epicatechin units are described. A potential electrophile and a nucleophile were connected with diester linkers and TMSOTf-catalyzed condensation was examined. In comparison with intermolecular catechin and catechin condensation, the intramolecular condensation required high reaction temperature and reversed 3,4-cis product was obtained. The condensed product was transformed into the natural 3,4-cis (+)-catechin-(4β→8)-(+)-catechin dimer.     

Effects of various triamines on cell-free polypeptide synthesis of Escherichia coli and on growth of its polyamine auxotrophs

The effects of various synthetic triamines having a general structure, H2N(CH2)xNH(CH2)yNH2, where x = 2-5 and y = 2-8 (abbreviated, x-y; with 3-4 being spermidine itself), on poly(U)-directed polypeptide synthesis of Escherichia coli and on growth of its polyamine-requiring mutants were examined in comparison with those of spermidine. Except for 2-2 and 2-3, all of the triamines stimulated more or less polypeptide synthesis at suboptimal Mg2+ concentrations, but the Mg2+ concentration required for the maximal stimulatory effect was different for each triamine. The degree of maximal stimulation caused by 3-3 (norspermidine), 4-4 (homospermidine), or 4-5 was nearly comparable with that by spermidine. The acetylspermidines were inactive, however, they inhibited the spermidine-stimulated polyphenylalanine synthesis. Many of the triamines examined reduced the ratio of leucine to phenylalanine incorporation into polypeptides during poly(U)-directed translation, and the degree of this effect did not necessarily correspond with that of the stimulatory effect. Moreover, 2-4, 2-5, 3-3 and 4-4 could stimulate the growth of a polyamine auxotroph of E. coli, MA 261, as effectively as did spermidine. However, 3-3 was the only triamine which could fully replaced spermidine in promoting growth of a mutant strain, KK 101, which is more dependent on polyamines than MA 261. Thus, these results demonstrated that some synthetic triamines were as active as spermidine in eliciting these effects, and also that there were some differences among these effects in the structural requirement for triamine.