Agricultural landscapes, including paddies, play an important role in maintaining biodiversity, but this biodiversity has been under the threat of toxic agro-chemicals. Our knowledge about how aquatic communities react to, and recover from, pesticides, particularly in relation to their residues, is deficient, despite the importance of such information for realistic environmental impact assessment of pesticides. The cumulative ecological impacts on aquatic paddy communities and their recovery processes after two successive annual applications of two systemic insecticides, imidacloprid and fipronil, were monitored between mid-May and mid-September each year. The abundance of benthic organisms during both years was significantly lower in both insecticide-treated fields than in the controls. Large-impacts of fipronil on aquatic arthropods were found after the two years. Growth of medaka fish, both adults and their juveniles, was affected by the application of the two insecticides. A Principal Response Curve analysis (PRC) showed the escalation and prolongation of changes in aquatic community composition by the successive annual treatments of each insecticide over two years. Residues of fipronil in soil, which are more persistent than those of imidacloprid, had a high level of impact on aquatic communities over time. For some taxonomic groups, particularly for water surface-dwelling and water-borne arthropods, the second annual treatment had far greater impacts than the initial treatment, indicating that impacts of these insecticides under normal use patterns cannot be accurately assessed during short-term monitoring studies, i.e., lasting less than one year. It is concluded that realistic prediction and assessment of pesticide effects at the community level should also include the long-term ecological risks of their residues whenever these persist in paddies over a year.

Differences in susceptibility of five cladocerans to the neonicotinoid imidacloprid and the phenyl-pyrazole fipronil, which have been dominantly used in rice fields of Japan in recent years, were examined based on short-term (48-h), semi-static acute immobilization exposure tests. Additionally, we compared the species sensitivity distribution (SSD) patterns of both insecticides between two sets of species: the five tested cladocerans and all other aquatic organisms tested so far, using data from the ECOTOX database of U.S. Environmental Protection Agency (USEPA). The sensitivity of the test species to either imidacloprid or fipronil was consistent, spanning similar orders of magnitude (100 times). At the genus level, sensitivities to both insecticides were in the following descending order: Ceriodaphnia > Moina > Daphnia. A positive relationship was found between body lengths of each species and the acute toxicity (EC(50)) of the insecticides, in particular fipronil. Differences in SSD patterns of imidacloprid were found between the species groups compared, indicating that test cladocerans are much less susceptible than other aquatic species including amphibians, crustaceans, fish, insects, mollusks and worms. However, the SSD patterns for fipronil indicate no difference in sensitivity between cladocerans tested and other aquatic organisms despite the greater exposure, which overestimates the results, of our semi-static tests. From these results, Ceriodaphnia sp. should be considered as more sensitive bioindicators (instead of the standard Daphnia magna) for ecotoxicological assessments of aquatic ecosystems. In addition, we propose that ecotoxicity data associated with differences in susceptibility among species should be investigated whenever pesticides have different physicochemical properties and mode of action.

The environmental risks of pesticides are typically determined by laboratory single-species tests based on OECD test guidelines, even if biodiversity should also be taken into consideration. To evaluate how realistic these assessments are, ecological changes caused by the systemic insecticides imidacloprid and fipronil, which have different physicochemical properties, when applied at recommended commercial rates on rice fields were monitored using experimental paddy mesocosms. A total of 178 species were observed. There were no significant differences in abundance of crop arthropods among the experimental paddies. However, zooplankton, benthic and neuston communities in imidacloprid-treated field had significantly less abundance of species than control and fipronil fields. Significant differences in abundance of nekton community were also found between both insecticide-treated paddies and control. Influences on the growth of medaka fish were also found in both adults and their fries. Both Principal Response Curve analysis (PRC) and Detrended Correspondence Analysis (DCA) showed the time series variations in community structure among treatments, in particular for imidacloprid during the middle stage of the experimental period. These results show the ecological effect-concentrations (LOEC ~ 1 μg/l) of these insecticides in mesocosms, especially imidacloprid, are clearly different from their laboratory tests. We suggest that differences in the duration of the recovery process among groups of species are due to different physicochemical properties of the insecticides. Therefore, realistic prediction and assessment of pesticide effects at the community level should consider not only the sensitivity traits and interaction among species but also the differences in physicochemical characteristics of each pesticide.

An efficient synthesis of bioactive chiral flavanones (1) was achieved through the Rh-catalyzed asymmetric 1,4-addition of arylboronic acid to chromone. The reaction in toluene proceeded smoothly at room temperature in the presence of 0.5% Rh catalyst with electron-poor chiral diphosphine MeO-F(12)-BIPHEP. In this reaction, the 1,2-addition to (S)-1 frequently occurred to yield (2S,4R)-2,4-diaryl-4-chromanol as a byproduct, which could be reduced by changing the reaction solvent to CH(2)Cl(2) to deactivate the Rh catalyst (3% required).

Stable isotopic compositions and elemental contents of the H, C, N, and O in 163 rice samples were analyzed. The samples were taken from three different farming countries; Japan (n = 103), United States of America (n = 30), and Australia (n = 21), in addition of Asian rice samples from Thailand (n = 2), Vietnam (n = 1), and China (n = 6) as comparison. They were mostly short grain samples known as "Koshihikari," with several samples of middle and long grains included. All samples were grown in the presence of either natural manure or artificial fertilizer. The climate of the rice farming environment was diverse, from arid to humid. Excluding deltaD data showing large uncertainty, according to the statistical analysis of the principal components based on the stable isotopic compositions such as delta(13)C, delta(15)N, and delta(18)O of rice samples, the Japanese rice samples were clearly distinctive from the Australian and the American rice samples. This fact may be explained by the regional differences in isotopic signatures of the climate, utilized nutrition, and/or quality of irrigation water among the farming countries. This statistical distinction could be one of the useful tools to extract the rice samples grown in Japan from those grown in the other countries.

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry of a model peptide, Substance P (SubP), was carried out using 2,4,6-trihydroxyacetophenone (THAP) and 2,4-dihydroxyacetophenone (DHAP) with cyclodextrins (cyclodextrin-supported matrix). It was found that the use of a cyclodextrin-supported matrix simplified the mass spectrum in the low-molecular-weight region. The interaction between THAP/DHAP and cyclodextrin (CD) was studied by UV-vis absorption spectroscopy and the incorporation of matrix molecules into the cyclodextrin cavity was confirmed by (1)H-NMR spectroscopy. DHAP showed tight incorporation with betaCD (betaCD(DHAP)) rather than THAP and it was found that the matrix-related peaks could be weakened by less than one third of the peak intensity of a protonated analyte. The betaCD(DHAP) matrix was applied to the measurements of two low-molecular-weight compounds; adenosine and adrenaline. It became clear that the cyclic structure of the CD and the host-guest interaction between betaCD and the matrix molecule were important to reduce the matrix-related peaks of THAP and DHAP.

The existence of the intermolecular interaction in CDCl(3) between oxygen of MeOH and the C(6)F(5) group is demonstrated.

Electron-poor chiral diphosphine ligands, MeO-F(28)-BIPHEP (1a) and MeO-F(12)-BIPHEP (1b), were synthesized for controlling a transition-metal catalyst electronically. The 1b-ligated Rh catalyst showed excellent catalytic activity with high % ee for asymmetric 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyls at 20 degrees C. The strong pi-acceptor ability of 1b induces transmetalation of arylboronic acid to catalyst precursor [RhCl(1b)](2) directly in the first step of the catalytic cycle.

An effective technique for the suppression of matrix-related ions in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry have been developed. Using typical organic matrices such as THAP (2,4,6-trihydroxyacetophenone) and CHCA (alpha-cyano-4-hydroxycinnamic acid) in a cyclodextrin cavity, we successfully measured the mass peaks of only protonated matrix ions and significantly suppressed their intensities and fragmentation. In addition, it became possible to analyze the mass peak of the analyte molecules (substance P and adenosine) without any interference from the matrix. We believe that this technique could be a powerful tool for MALDI mass spectrometry, particularly for low-molecular-weight compounds.