Measurement of the tau lepton mass and an upper limit on the mass difference between tau+ and tau-

The mass of the tau lepton has been measured in the decay mode tau-->3pinutau using a pseudomass technique. The result obtained from 414 fb-1 of data collected with the Belle detector is Mtau=[1776.61+/-0.13(stat)+/-0.35(sys)] MeV/c2. The upper limit on the relative mass difference between positive and negative tau leptons is |Mtau+-Mtau-|/Mtau<2.8 x 10-4 at 90% confidence level.     

Formal Synthesis of Sarain A: Intramolecular Cycloaddition of an Eight‐Membered Cyclic Nitrone to Construct the 2‐Azabicyclo[3.3.1]nonane Framework

An enantioselective route to the tetracyclic skeleton of sarain A has been developed. Asymmetric reduction of an ynone introduced a chiral center which was transferred to the contiguous tertiary stereogenic centers through an Ireland–Claisen rearrangement. The 2‐azabicyclo[3.3.1]nonane framework was constructed by an unprecedented intramolecular cycloaddition of an eight‐membered cyclic nitrone. Using the steric bias of the bicyclic system, the quaternary carbon atom was constructed by a stereoselective aldol reaction. Further ring formations were performed by ring‐closing metathesis for the 13‐membered ring and an iodoamidation reaction for the pyrrolidine ring. The present synthesis has successfully provided an alternative route to the late‐stage intermediate of Overman’s synthesis.     

Total Synthesis of Proposed Structure of Yuremamine and All Diastereomers Using [3+2]‐Cycloaddition of Platinum‐Containing Azomethine Ylide

Total synthesis of the proposed structure of yuremamine has been achieved for the first time based on the intermolecular [3+2]‐cycloaddition reaction of the platinum‐containing azomethine ylide. All the possible diastereomers of yuremamine were also synthesized via the common intermediate. Through these syntheses, it was confirmed that the proposed structure of yuremamine and the diastereomers differ from the natural product.     

Asymmetric Total Synthesis of ent‐Pyripyropene A

An asymmetric total synthesis of ent‐pyripyropene A was achieved by a convergent synthetic route. We used our originally developed Ti^III‐catalyzed radical cyclization to construct an AB‐ring portion that consisted of a trans‐decalin skeleton with five contiguous stereogenic centers. The coupling between the AB‐ring and the DE‐ring portions, and a subsequent C‐ring cyclization, led to the total synthesis of ent‐pyripyropene A. An evaluation of the insecticidal activity of ent‐pyripyropene A against two aphid species revealed that ent‐pyripyropene A was 35–175 times less active than naturally occurring pyripyropene A. This result indicated that the biological target of pyripyropene A recognizes the absolute configuration of pyripyropene A.     

CesA protein is included in the terminal complex of <Emphasis Type="Italic">Acetobacter</Emphasis>

Cellulose is a major biopolymer on the earth that is produced by cellulose synthase in the cell membrane of living organisms. Cellulose synthase is a hetero-subunit complex composed of several different protein subunits, and is visualized as a supermolecular complex called a “terminal complex” by electron microscopy. Such supermolecular organization of an enzyme complex is believed to be important for the fiber formation or crystallization of cellulose microfibrils in cellulose biosynthesis. In the case of the cellulose-producing bacterium Acetobacter, it is hypothesized that the enzyme complex includes at least six subunits given its genetic constitution. However, to date, only three of these molecules have been experimentally confirmed as the subunits included in the terminal complex: CesB, CesD, and ccp2. In this study, we used fluorescence immuno-microscopy to show that CesA protein, the catalytic subunit, is included in the terminal complex of Acetobacter. Furthermore we discuss the obtained microscopic data for improving our understanding of the molecular organization of the bacterial cellulose synthase complex.     

Third-order nonlinear optical properties of open-shell supermolecular systems composed of acetylene linked phenalenyl radicals

The third-order nonlinear optical (NLO) properties, at the molecular level, the static second hyperpolarizabilities, γ, of supermolecular systems composed of phenalenyl and pyrene rings linked by acetylene units are investigated by employing the long-range corrected spin-unrestricted density functional theory, LC-UBLYP, method. The phenalenyl based superethylene, superallyl, and superbutadiene in their lowest spin states have intermediate diradical characters and exhibit larger γ values than the closed-shell pyrene based superpolyene systems. The introduction of a positive charge into the phenalenyl based superallyl radical changes the sign of γ and enhances its amplitude by a factor of 35. Although such sign inversion is also observed in the allyl radical and cation systems in their ground state equilibrium geometries, the relative amplitude of γ is much different, that is, |γ(regular allyl cation)/γ(regular allyl radical)| = 0.61 versus |γ(phenalenyl based superallyl cation)/γ(phenalenyl based superallyl radical)| = 35. In contrast, the model ethylene, allyl radical/cation, and butadiene systems with stretched carbon-carbon bond lengths (2.0 ?), having intermediate diradical characters, exhibit similar γ features to those of the phenalenyl based superpolyene systems. This exemplifies that the size dependence of γ as well as its sign change by introducing a positive charge on the phenalenyl based superpolyene systems originate from their intermediate diradical characters. In addition, the change from the lowest to the highest π-electron spin states significantly reduces the γ amplitudes of the neutral phenalenyl based superpolyene systems. For phenalenyl based superallyl cation, the sign inversion of γ (from negative to positive) is observed upon switching between the singlet and triplet states, which is predicted to be associated with a modification of the balance between the positive and negative contributions to γ. The present study paves the way toward designing a variety of open-shell NLO supermolecular systems composed of phenalenyl radical building blocks.     

Palladium-catalyzed denitrogenation reaction of 1,2,3-benzotriazin-4(3H)-ones incorporating isocyanides

1,2,3-Benzotriazin-4(3H)-ones and 1,2,3,4-benzothiatriazine 1,1(2H)-dioxide reacted with isocyanides in the presence of a palladium catalyst to give 3-(imino)isoindolin-1-ones and 3-(imino)thiaisoindoline 1,1-dioxides, respectively, in high yield. An intermediate azapalladacycle was generated through denitrogenation of the triazine moiety, and an isocyanide was incorporated therein.     

A new method for aromatic difluoromethylation: copper-catalyzed cross-coupling and decarboxylation sequence from aryl iodides

A new methodology for aromatic difluoromethylation is described. Aryl iodides reacted with α-silyldifluoroacetates upon treatment with copper catalyst in DMSO or DME to give the corresponding aryldifluoroacetates in moderate to good yields. The subsequent hydrolysis of aryldifluoroacetates and KF-promoted decarboxylation afforded a variety of difluoromethyl aromatics.     

A clinical trial for therapeutic drug monitoring using microchip-based fluorescence polarization immunoassay

Microchip analysis is a promising method for therapeutic drug monitoring. This led us to evaluate a microchip-based fluorescence polarization immunoassay (FPIA) system for point-of-care testing on patients being treated with theophylline. The sera were collected from 20 patients being treated with theophylline. Fluorescence polarization was measured on the microchip and theophylline concentrations in serum were obtained. Regression analysis of the correlations was done between the results given by the microchip-based FPIA and the conventional cloned enzyme donor immunoassay (CEDIA), and between the results given by the microchip-based FPIA and the conventional particle-enhanced turbidimetric inhibition immunoassay (PETINIA). We successfully carried out a quantitative analysis of theophylline in serum at values near its therapeutic range in 65 s. The results obtained by the microchip-based FPIA correlated well with CEDIA and PETINIA results; the correlation coefficients (R ²) were 0.986 and 0.989, respectively. The FPIA system is a simple and rapid method for point-of-care testing of drugs in serum, and its accuracy is the same as the conventional CEDIA and PETINIA. It is essential to use real samples from patients and to confirm good correlations with conventional methods for a study on the realization of microchip.