Enantioselective Synthesis of Ipsenol and Ipsdienol Using a (2-Bromoallyl)borane Derivative

(S)-(-)-Ipsenol (2b) and (S)-(+)-ipsdienol (4b), a major component of the sex pheromone of the bark beetle, and their enantiomers (3b and 5b) were prepared enantioselectively using tartrate esters of (2-bromoallyl)boronic acid in the key step.

     

Open-sandwich immunoassay for sensitive and broad-range detection of a shellfish toxin gonyautoxin

At present, the analytical method for paralytic shellfish poisoning (PSP) toxins in shellfish is the mouse bioassay (MBA), which is an official method of the Association of Analytical Communities (AOAC [8]). However, the low sensitivity and concerns over the number of live animals required for testing have been cited as the major reason for seeking its replacement. In this report, we employed an open-sandwich immunoassay (OS-IA) to detect gonyautoxin (GTX2/3), a kind of PSP toxins. OS-IA, which utilizes the antigen-induced enhancement of antibody V_H/V_L interaction, can measure a small molecule antigen in a noncompetitive format. Hence it has a wider working range and shorter measurement time. We isolated anti-GTX2/3 antibody gene from a hybridoma GT-13A by screening a Fab-displaying phage library. Then the vectors for OS-IA were constructed, and examined for antigen concentration-dependency of the V_H/V_L interaction by OS-ELISA. As a result, in each case, signal intensity increases notably in a wide concentration range (0.1 to >1000 ng mL⁻¹) of free GTX2/3, which was enough to cover its regulation value (80 μg 100 g⁻¹) in many countries. So OS-IA will be widely applicable to detect PSP toxins in shellfish meats and in drinking water.     

CdS and Cd carboxylate nanoclusters dispersed in polymer matrix produced by a freeze drying method

Cadmium sulfide (CdS) nanoclusters were prepared by a freeze drying method from two types of cadmium carboxylates. One was cadmium methacrylates that were part of poly(methyl methacrylate) (PMMA) ionomer. The other was cadmium acetates that were dispersed in PMMA. X-ray diffraction was mainly used to study the formation and the size of nanoclusters. The size of CdS made from the ionomer was 0.9 nm, whereas that from the composite of cadmium acetate and PMMA was 2 nm. This was consistent with the size difference of the precursors of CdS: i.e., Cd carboxylate nanoclusters (ionic aggregates) were smaller in the ionomer than in the PMMA mixture, because ionic groups in the ionomer were constrained due to their connectivity to backbone chains and thus forming smaller ionic aggregates. Once stabilized, however, CdS nanocluster sizes were unchanged despite thermal treatments at up to 220 °C for 24 h for both systems. Structural transformations from a freeze dried cadmium carboxylate powder, to a CdS-containing powder, and to a heat-treated CdS-containing sample are speculated for both types of systems.     

Mechanistic study of asymmetric Michael addition of malonates to enones catalyzed by a primary amino acid lithium salt

A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher enantioselectivity than that achieved with the corresponding catalysts derived from α- and γ-amino acids for this reaction. Detailed studies of the transition states with DFT calculations revealed that the lithium cation and carboxylate group of the β-amino acid salt catalyst have important roles in achieving high enantioselectivity in the Michael addition reaction of malonates to enones.     

Determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry using Pd/Mg chemical modifier and slurry sampling

Effectiveness of Pd/Mg chemical modifier for the accurate direct determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry (GF-AAS) using slurry samples was evaluated. A calibration curve prepared by aqueous zinc standard solution with addition of Pd/Mg chemical modifier is used to determine the zinc concentration in the sediment. The accuracy of the proposed method was confirmed using Certified Reference Materials, NMIJ CRM 7303-a (lacustrine sediment) from National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology, Japan, and MESS-3 (marine sediment) and PACS-2 (marine sediment) from National Research Council, Canada. The analytical results obtained by employing Pd/Mg modifier are in good agreement with the certified values of all the reference sediment materials. Although for NRC MESS-3 an accurate determination of zinc is achieved even without the chemical modifier, the use of Pd/Mg chemical modifier is recommended as it leads to establishment of a reliable and accurate direct analytical method. One quantitative analysis takes less than 15 minutes after we obtain dried sediment samples, which is several tens of times faster than conventional analytical methods using acid digested sample solutions. The detection limits are 0.13?µg?g^?1 (213.9?nm) and 16?µg?g^?1 (307.6?nm), respectively, in sediment samples, when 40?mg of dried powdered samples are suspended in 20?mL of 0.1?mol?L^?1 nitric acid and a 10?µl portion of the slurry sample is measured. The precision of the proposed method is 8–15% (RSD).     

Improvement of TiO2/Dye/Electrolyte Interface Conditions by Positional Change of Alkyl Chains in Modified Panchromatic Ru Complex Dyes

A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation.     

Protective Effect of Ferulic Acid against Hydrogen Peroxide Induced Apoptosis in PC12 Cells

Ferulic Acid (FA) is a highly abundant phenolic phytochemical which is present in plant tissues. FA has biological effects on physiological and pathological processes due to its anti-apoptotic and anti-oxidative properties, however, the detailed mechanism(s) of function is poorly understood. We have identified FA as a molecule that inhibits apoptosis induced by hydrogen peroxide (H₂O₂) or actinomycin D (ActD) in rat pheochromocytoma, PC12 cell. We also found that FA reduces H₂O₂-induced reactive oxygen species (ROS) production in PC12 cell, thereby acting as an anti-oxidant. Then, we analyzed FA-mediated signaling responses in rat pheochromocytoma, PC12 cells using antibody arrays for phosphokinase and apoptosis related proteins. This FA signaling pathway in PC12 cells includes inactivation of pro-apoptotic proteins, SMAC/Diablo and Bad. In addition, FA attenuates the cell injury by H₂O₂ through the inhibition of phosphorylation of the extracellular signal-regulated kinase (ERK). Importantly, we find that FA restores expression levels of brain-derived neurotrophic factor (BDNF), a key neuroprotective effector, in H₂O₂-treated PC12 cells. As a possible mechanism, FA increases BDNF by regulating microRNA-10b expression following H₂O₂ stimulation. Taken together, FA has broad biological effects as a neuroprotective modulator to regulate the expression of phosphokinases, apoptosis-related proteins and microRNAs against oxidative stress in PC12 cells.     

Measurements of branching fractions for B --> K pi and B --> pi pi decays

We report measurements of branching fractions for B --> K pi and B --> pi pi decays based on a data sample of 449 x 10(6) BB[over] pairs collected at the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. We also measure the ratios of partial widths for B-->Kpi decays, namely R(c) identical with 2Gamma(B(+) --> K(+) pi(0))/Gamma(B(+) --> K(0) pi(+)) = 1.08+/-0.06+/-0.08 and R(n) identical with Gamma(B(0) --> K(+) pi(-))/2 Gamma(B(0) --> K(0) pi(0)) = 1.08+/-0.08+/-0.08, where the first and the second errors are statistical and systematic, respectively. These ratios are sensitive to enhanced electroweak penguin contributions from new physics; the new measurements are, however, consistent with standard model expectations.     

Measurement of inclusive Ds, D0, and J/psi rates and determination of the Bs(*)Bs(*) production fraction in bb Events at the Upsilon(5S) resonance

The inclusive production of D(s), D(0), and J/psi mesons is studied using a 1.86 fb(-1) data sample collected on the Upsilon(5S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. The number of bb events in this Upsilon(5S) data sample is determined. We measure the branching fractions B(Upsilon(5S)-->D(s)X)/2=(23.6+/-1.2+/-3.6)%, B(Upsilon(5S)-->D(0)X)/2=(53.8+/-2.0+/-3.4)%, and B(Upsilon(5S)-->J/psiX)/2=(1.030+/-0.080+/-0.067)%. From the D(s) and D(0) inclusive branching fractions the ratio f(s)=(18.0+/-1.3+/-3.2)% of B(s)(*)B(s)(*) to the total bb quark pair production at the Upsilon(5S) energy is obtained in a model-dependent way.     

Observation of time-dependent CP violation in B0 --> eta'K0 decays and improved measurements of CP asymmetries in B0 --> phiK0, KS0KS0KS0 and B0 --> J/psiK0 decays

We present improved measurements of CP-violation parameters in B(0) --> phiK(0), eta(')K(0), KS(0)KS(0)KS(0) decays based on a sample of 535 x 10(6) BB pairs collected at the Upsilon(4S) resonance with the Belle detector at the KEKB energy-asymmetric e(+)e(-) collider. We obtain sin2phi1(eff)=+0.64+/-0.10(stat)+/-0.04(syst) for B(0) --> eta(')K(0), +0.50+/-0.21(stat)+/-0.06(syst) for B(0) --> phiK(0), and +0.30+/-0.32(stat)+/-0.08(syst) for B(0) --> KS(0)KS(0)KS(0) decays. We have observed CP violation in the B(0) --> eta(')K(0) decay with a significance of 5.6 standard deviations. We also perform an improved measurement of CP asymmetries in B(0) --> J/psiK(0) decays and obtain sin2phi1=+0.642+/-0.031(stat)+/-0.017(syst).