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.     

Observation of a charmoniumlike state produced in association with a J/psi in e+e- annihilation at sqrt[s] approximately equal to 10.6 GeV

We report the first observation of a charmoniumlike state recoiling from the J/psi in the inclusive process e+e- -->J/psi+anything at a mass of (3.943+/-0.006+/-0.006) GeV/c{2}. We also observe the decay of this state into D*D[over ] and determine its intrinsic width to be less than 52 MeV/c{2} at the 90% C.L. These results are obtained from a 357 fb{-1} data sample collected with the Belle detector near the Upsilon(4S) resonance, at the KEKB asymmetric-energy e+e- collider.     

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.     

Non‐Heme Dioxygenase Catalyzes Atypical Oxidations of 6,7‐Bicyclic Systems To Form the 6,6‐Quinolone Core of Viridicatin‐Type Fungal Alkaloids

The 6,6‐quinolone scaffold of the viridicatin‐type of fungal alkaloids are found in various quinolone alkaloids which often exhibit useful biological activities. Thus, it is of interest to identify viridicatin‐forming enzymes and understand how such alkaloids are biosynthesized. Here an Aspergillal gene cluster responsible for the biosynthesis of 4′‐methoxyviridicatin was identified. Detailed in vitro studies led to the discovery of the dioxygenase AsqJ which performs two distinct oxidations: first desaturation to form a double bond and then monooxygenation of the double bond to install an epoxide. Interestingly, the epoxidation promotes non‐enzymatic rearrangement of the 6,7‐bicyclic core of 4′‐methoxycyclopenin into the 6,6‐quinolone viridicatin scaffold to yield 4′‐methoxyviridicatin. The finding provides new insight into the biosynthesis of the viridicatin scaffold and suggests dioxygenase as a potential tool for 6,6‐quinolone synthesis by epoxidation of benzodiazepinediones.     

Ultrafast Encapsulation of Metal Nanoclusters into MFI Zeolite in the Course of Its Crystallization: Catalytic Application for Propane Dehydrogenation

Encapsulating metal nanoclusters into zeolites combines the superior catalytic activity of the nanoclusters with high stability and unique shape selectivity of the crystalline microporous materials. The preparation of such bifunctional catalysts, however, is often restricted by the mismatching in time scale between the fast formation of nanoclusters and the slow crystallization of zeolites. We herein demonstrate a novel strategy to overcome the mismatching issue, in which the crystallization of zeolites is expedited so as to synchronize it with the rapid formation of nanoclusters. The concept was demonstrated by confining Pt and Sn nanoclusters into a ZSM-5 (MFI) zeolite in the course of its crystallization, leading to an ultrafast, in situ encapsulation within just 5 min. The Pt/Sn-ZSM-5 exhibited exceptional activity and selectivity with stability in the dehydrogenation of propane to propene. This method of ultrafast encapsulation opens up a new avenue for designing and synthesizing composite zeolitic materials with structural and compositional complexity.     

Dehydration‐fragmentation mechanism of cathinones and their metabolites in ESI‐CID

Various cathinone‐derived designer drugs (CATs) have recently appeared on the drug market. This study examined the mechanism for the generation of dehydrated ions for CATs during electrospray ionization collision‐induced dissociation (ESI‐CID). The generation mechanism of dehydrated ions is dependent on the amine classification in the cathinone skeleton, which is used in the identification of CATs. The two hydrogen atoms eliminated during the dehydration of cathinone (primary amine) and methcathinone (secondary amine) were determined, and the reaction mechanism was elucidated through the deuterium labeling experiments. The hydrogen atom bonded to the amine nitrogen was eliminated with the proton added during ESI, in both of the tested compounds. This provided evidence that CATs with tertiary amine structures (such as dimethylcathinone and α‐pyrrolidinophenones [α‐PPs]) do not undergo dehydration. However, it was shown that the two major tertiary amine metabolites (1‐OH and 2″‐oxo) of CATs generate dehydrated ions in ESI‐CID. The dehydration mechanisms of the metabolites of α‐pyrrolidinobutiophenone (α‐PBP) belongs to α‐PPs were also investigated. Stable‐isotope labeling showed the dehydration of the 1‐OH metabolite following a simple mechanism where the hydroxy group was eliminated together with the proton added during ESI. In contrast, the dehydration mechanism of the 2″‐oxo metabolite involved hydrogen atoms in three or more locations along with the carbonyl group oxygen, indicating that dehydration occurred via multiple mechanisms likely including the rearrangement reaction of hydrogen atoms. These findings presented herein indicate that the dehydrated ions in ESI‐CID can be used for the structural identification of CATs.     

Mechanical C−C Bond Formation by Laser Driven Shock Wave

Mechanically induced C−C bond formation was demonstrated by the laser driven shock wave generated in liquid normal alkanes at room temperature. Gas chromatography mass spectrometry analysis revealed the dehydrogenation condensation between two alkane molecules, for seven normal alkanes from pentane to undecane. Major products were identified to be linear and branched alkane molecules with double the number of carbons, and exactly coincided with the molecules predicted by supposing that a C−C bond was formed between two starting molecules. The production of the alkane molecules showed that the C−C bond formation occurred almost evenly at all the carbon positions. The dependence of the production on the laser pulse energy clearly indicated that the process was attributed to the shock wave. The C−C bond formation observed was not a conventional passive chemical reaction but an unprecedented active reaction.     

Reductive coupling of N-methoxycarbonyl lactams with benzophenone and 9-fluorenone by low-valent titanium

The reductive coupling of N-methoxycarbonyl lactams with benzophenone by Zn-TiCl₄ in THF gave cross-coupled products as cyclic α-diphenylidene-N-methoxycarbonylamines and ring-opening α,α-diphenyl-α-hydroxy-ω-(N-methoxycarbonyl)amino ketones selectively depending on the reduction conditions. The reductive coupling of N-methoxycarbonyl lactams with 9-fluorenone by Zn-TiCl₄ gave cyclic α-(9H-fluoren-9-ylidene)-N-methoxycarbonylamines preferentially irrespective to the conditions.