Biotransformation of ferulic acid into two new dihydrotrimers by Momordica charantia peroxidase

As a result of a continuing investigation of the biotransformation of ferulic acid with H2O2/Momordica charantia peroxidase at pH 5.0 in the presence of acetone, triFA1 (1) and triFA2 (2), two new FA dehydrotrimers, have been isolated. The structures were elucidated from the spectroscopic data including 2D-NMR such as HSQC, HMBC and NOESY data. TriFA1 (1) is a unique FA dehydrotrimer possessing a 3a,9b-dihydro-1H-furo[3,4-c][1]benzopyran-3(4H)-one ring system. The possible mechanism for the formation of triFA1 was also discussed.     

Measurement of neutrino oscillation with KamLAND: evidence of spectral distortion

We present results of a study of neutrino oscillation based on a 766 ton/year exposure of KamLAND to reactor antineutrinos. We observe 258 nu (e) candidate events with energies above 3.4 MeV compared to 365.2+/-23.7 events expected in the absence of neutrino oscillation. Accounting for 17.8+/-7.3 expected background events, the statistical significance for reactor nu (e) disappearance is 99.998%. The observed energy spectrum disagrees with the expected spectral shape in the absence of neutrino oscillation at 99.6% significance and prefers the distortion expected from nu (e) oscillation effects. A two-neutrino oscillation analysis of the KamLAND data gives Deltam(2)=7.9(+0.6)(-0.5)x10(-5) eV(2). A global analysis of data from KamLAND and solar-neutrino experiments yields Deltam(2)=7.9(+0.6)(-0.5)x10(-5) eV(2) and tan((2)theta=0.40(+0.10)(-0.07), the most precise determination to date.     

Coexistence of two different anion states in polyacene nanocluster anions

Two types of anion states are shown to coexist in nanometer-scale polyacene cluster anions. Naphthalene and anthracene nanoclusters having a single excess electron were produced in the gas-phase. Photoelectron spectra of size-selected cluster anions containing 2 to 100 molecules revealed that rigid "crystal-like" cluster anions emerge, greater than approximately 2 nanometers in size, and coexist with the "disordered" cluster anion in which the surrounding neutral molecules are reorganizing around the charge core. These two anion states appear to be correlated to negative polaronic states formed in the corresponding crystals.     

Oxidation-active flavin models: oxidation of alpha-hydroxy acids by benzo-dipteridine bearing metal-binding site in the presence of divalent metal ion and base in organic solvents.

The oxidizing ability of benzo-dipteridine bearing a bipyridin-6-ylmethyl moiety (4) was found to be increased with Zn(2+) by approximately 10(3)-fold for sulfite addition in MeOH and approximately 10(2)-fold for oxidation of an NADH model in MeCN. It was found for the first time that 4 is able to oxidize alpha-hydroxy acids to alpha-keto acids in the presence of a divalent metal ion such as Zn(2+), Co(2+), and Ni(2+) and an amine base in MeCN or t-BuOH, whereas benzo-dipteridine having a bipyridin-5-ylmethyl moiety (3) is unable to oxidize them under the same conditions. The oxidation reaction was kinetically investigated including the kinetic isotope effect for deuterated mandelic acids (k(H)/k(D) = 2.1-3.7) and the Hammett plots for substituted mandelic acids (V-shaped plots). In the reaction of alpha-substituted alpha-hydroxy acids such as alpha-methyl mandelic and benzylic acids with 4, novel oxidative decarboxylation was found to take place, giving acetophenone and benzophenone, respectively. The oxidation mechanism for mandelic acid was proposed to proceed via a ternary complex of 4.Zn(2+).PhCH(OH)CO(2)(-), in which alpha-oxyanion of mandelate attacks C(4a)-position of 4 to form an adduct followed by 1,2-elimination to afford benzoyl formate and 2e-reduced 4. The roles of the metal ion were proposed as follows; (i) activation of 4, (ii) substrate-binding site, and (iii) activation of the bound alpha-hydroxy acid by lowering pK(a)'s of alpha-OH and alpha-CH. This is a first example that a flavin model oxidizes alpha-hydroxy acids in the presence of a metal ion.