Effect of Intertidal Elevation at Tsuyazaki Cove, Fukuoka, Japan on Survival Rate of Horseshoe Crab Tachypleus tridentatus Eggs.

Physical factors affecting the survival of Tachypleus tridentatus eggs were investigated by translocating their eggs between the high intertidal zone and the low intertidal zone of a known spawning site. The mean egg survival rates per day were highest in the mid intertidal zone (45.1%±25.4%) and the lowest in the low intertidal zone (13.3%±27.6%). Differences in the elevation, air exposure time, and water content of the spawning ground were significant factors determining the egg survival rates. Excessive or insufficient air exposure time resulted in inadequate water content at higher and lower intertidal zones and could reduce egg survival. On the other hand, moderate saturation and dehydration were repeated with each tidal movement in the mid intertidal zone. This dynamic is considered as one of the crucial factors for the survival of eggs and is considered optimal for spawning. Therefore, the protection of the mid intertidal zone is imperative for maximizing the egg survival rate in Tsuyazaki Cove where almost all suitable nesting sites have disappeared due to coastal development. By protecting these optimal sites for spawning and recovering other optimal sites on suitable beaches, a positive contribution can be made to future management and conservation. The study also suggests that translocating eggs from marginal to optimal spawning sites might be a recovery strategy for this globally endangered species.

Field response of male pine sawflies, Neodiprion sertifer (Diprionidae), to sex pheromone analogs in Japan and Sweden.

The pine sawfly Neodiprion sertifer (Geoffroy) uses the acetate or propionate of (2S,3S,7S)-3,7-dimethyl-2-pentadecanol (diprionol) as pheromone components, with the (2S,3R,7R)-isomer being antagonistic, synergistic, or inactive according to the population tested. In this study, we tested the attraction of males to the acetates of three analogs of diprionol, each missing one methyl group, viz. (2S,7S)-7-methyl-2-pentadecanol, (2S,6S)-2,6-dimethyl-1-tetradecanol, and (2S,3S)-3-methyl-2-pentadecanol. None of the analogs alone, or in combination with diprionol acetate, was attractive in Sweden, even at 100 times the amount of diprionol acetate attractive to N. sertifer. In Japan, the acetate of (2S,3S)-3-methyl-2-pentadecanol attracted males when tested in amounts 10-20 times higher than the acetate pheromone component. The acetate esters of the (2S,3R)-analog and the (2S,3R,7R)-isomer of diprionol also were tested in combination with the pheromone compound (acetate ester). Both compounds caused an almost total trap-catch reduction in Sweden, whereas in Japan they appear to have relatively little effect on trap capture when added to diprionol acetate. Butyrate and iso-butyrate esters of diprionol were unattractive to N. sertifer in Sweden. In summary, there exists geographic variation in N. sertifer in responses to both diprionyl acetate and some of its analogs.

Short-term dynamics of cyanobacterial toxins (microcystins) following a discharge from a coastal reservoir in Isahaya Bay, Japan.

Freshwater cyanobacteria produce highly toxic substances such as microcystins (MCs), and water containing MCs is often discharged to downstream and coastal areas. We conducted field monitoring in Isahaya Bay to clarify the short-term dynamics of MCs discharged from a reservoir following a cyanobacteria bloom in the warm season. MCs were detected in the seawater of the bay (max. 0.10 µg L(-1)), and were deposited on the sea floor, with the MC content of the surface sediment increasing by approximately five times (0.11±0.077-0.53±0.15 µg kgww(-1), mean±SD) at the four stations near the reservoir drainage gate before and after the discharge. The MCs was then transported from the mouth of the bay by tidal currents during the period of the study. Therefore, the MCs were moved away from the closed water area where the cyanobacteria blooms, and spread throughout the coastal area.

A Stereochemical Study of the Isomerization of Cyclopropyl Ethers to Allyl Ethers Catalyzed with Zinc Iodide.

Optically active 1-alkoxybicyclo[4.1.0]heptane was converted using zinc iodide as a catalyst to 2-alkoxymethylidenecyclohexane without loss of optical purity. The mechanism of the isomerization was studied using a stereochemical analysis of the product and deuterium labeling experiments. The results indicated that the isomerization takes place through a stepwise mechanism that involves an attack of zinc iodide on the cyclopropane ring to cause ring opening, followed by an intramolecular 1,2-hydride shift with liberation of the zinc iodide.

Unique dual fluorescence of sterically congested hexaalkyl benzenehexacarboxylates: mechanism and application to viscosity probing.

The static and dynamic fluorescence behavior of a series of hexaalkyl benzenehexacarboxylates (R(6)BHC; R = methyl (Me), tert-butyl (tBu), (-)-menthyl (Men), (-)-bornyl (Bor), (-)-1-methylheptyl (MHp), neopentyl (neoPn), and 2-adamantyl (Ad)) was studied by steady-state and time-resolved fluorescence spectroscopy. Dual fluorescence from both the partially relaxed metastable Franck-Condon-like (FC') and the fully relaxed (RX) state was observed for tBu(6)BHC, Men(6)BHC, Bor(6)BHC, MHp(6)BHC, neoPn(6)BHC, and Ad(6)BHC, whereas only single fluorescence from the RX state was observed for Me(6)BHC. Picosecond time-resolved fluorescence spectroscopic measurements clearly demonstrated that the initially formed Franck-Condon (FC) state sequentially converts to the FC' and then to RX state, with the relaxation hindered to such an extent that it shows variation with the steric bulk of the R groups. Thus, the fluorescence lifetimes (tau's) of FC' and RX are critically dependent on the bulkiness of the R groups, varying from 17 to 130 ps and from 0.6 to 1.1 ns, respectively. The relative intensity of FC' and RX fluorescence (I(RX)/I(FC)(')) was found to be dependent on the excitation wavelength, suggesting that the conformational relaxation from the FC' to RX state can compete with the vibrational relaxation of the FC' state. The temperature and pressure dependences were studied by steady-state fluorescence spectroscopy to give the activation energies of 1-3 kcal/mol for the FC'-to-RX relaxation of congested R(6)BHCs, as well as the activation volumes of 2.0, -0.62, and 7.4 mL/mol for tBu(6)BHC, Men(6)BHC, and Bor(6)BHC at room temperature. The fluorescence anisotropy (rho), as a measure of molecular motion, was also determined to be in the ranges of 0.03-0.3 for FC' and 0.003-0.01 for RX. The much larger rho's for the FC' fluorescence by a factor of 2-100 are attributed to the shorter tau's. The I(RX)/I(F' ratio was found to be insensitive to solvent polarity, but critically dependent on solvent viscosity, exhibiting an excellent linear relationship with the reciprocal viscosity. The potential use of these sterically congested R(6)BHCs as microenvironmental viscosity probes is proposed.

"Chiral perturbation factor" approach reveals importance of entropy term in stereocontrol of the 2,4-pentanediol-tethered reaction.

The stereocontrol mechanism of the 2,4-pentanediol (PD)-tethered reaction was studied in detail using a reaction system consisting of phenyl and rhodium carbenoid moieties. Different tethers were examined to analyze the effects of the methyl groups on the PD tether. Among the reactions with these tethers, the PD tether achieves an unmeasurably high stereoselectivity in a diastereomeric ratio of >500. Another tether showing a high but measurable stereoselectivity in a ratio of 41 is mostly controlled by the entropy term. To clarify the role of the methyl groups on the chiral tethers, which are the origin of the stereocontrol, the "chiral perturbation factor" is introduced. This parameter is defined as the rate of a chiral reaction relative to that of an achiral reference reaction. By analyzing the temperature dependence of the chiral perturbation factors for different chiral-tethered reactions, high potentials of the PD-tethered reaction in its stereocontrol are concluded to be due to the entropy term.