Synthesis of (S)-γ-Lactones with a Combination of Lipase-Catalyzed Resolution and Mitsunobu Reaction

Six kinds of (S)-γ-lactones [e.g., (S)-γ-decalactone, (S)-γ-undecalactone, and (S)-γ-jasmolactone] were synthesized with 71–88% yields and >97% optical purities by combining lipase-catalyzed resolution with the Mitsunobu reaction.     

Combination of Novozym 435–Catalyzed Hydrolysis and Mitsunobu Reaction for Production of (R)-γ-Lactones

Chiral γ-lactones of both enantiomers were synthesized with more than 90% optical purities. The key step was Novozym 435–catalyzed hydrolysis of racemic N-benzyl-4-acetoxyalkylamides. Additionally, because (R)-γ-lactones are predominant in apricot, mango, peach, passion fruit, and strawberry, synthesis was attempted using only one enantiomer selectively. The (R)-enantimer was synthesized with more than 80% total yield and more than 90% optical purity by a combination of Novozym 435–catalyzed hydrolysis and the Mitsunobu reaction.     

Application of plug–plug technique to ACE experiments for discovery of peptides binding to a larger target protein: A model study of calmodulin‐binding fragments selected from a digested mixture of reduced BSA

To discover peptide ligands that bind to a target protein with a higher molecular mass, a concise screening methodology has been established, by applying a “plug–plug” technique to ACE experiments. Exploratory experiments using three mixed peptides, mastoparan‐X, β‐endorphin, and oxytocin, as candidates for calmodulin‐binding ligands, revealed that the technique not only reduces the consumption of the protein sample, but also increases the flexibility of the experimental conditions, by allowing the use of MS detection in the ACE experiments. With the plug–plug technique, the ACE–MS screening methodology successfully selected calmodulin‐binding peptides from a random library with diverse constituents, such as protease digests of BSA. Three peptides with K_d values between 8–147 μM for calmodulin were obtained from a Glu‐C endoprotease digest of reduced BSA, although the digest showed more than 70 peaks in its ACE–MS electropherogram. The method established here will be quite useful for the screening of peptide ligands, which have only low affinities due to their flexible chain structures but could potentially provide primary information for designing inhibitors against the target protein.     

Energy-dependent tunneling from few-electron dynamic quantum dots

We measure the electron escape rate from surface-acoustic-wave dynamic quantum dots (QDs) through a tunnel barrier. Rate equations are used to extract the tunneling rates, which change by an order of magnitude with tunnel-barrier-gate voltage. We find that the tunneling rates depend on the number of electrons in each dynamic QD because of Coulomb energy. By comparing this dependence to a saddle-point-potential model, the addition energies of the second and third electron in each dynamic QD are estimated. The scale ( approximately a few meV) is comparable to those in static QDs as expected.     

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.     

Construction of Helically Stacked π-Electron Systems in Poly(quinolylene-2,3-methylene) Stabilized by Intramolecular Hydrogen Bonds

π-Stacked polymers, which consist of layered π-electron systems in a polymer, can be expected to be used in molecular electronic devices. However, the construction of a stable π-stacked structure in a polymer is considerably challenging because it requires sophisticated designs and precise synthetic methods. Herein, we present a novel π-stacked architecture based on poly(quinolylene-2,3-methylene) bearing alanine derivatives as the side chain, obtained through the living cyclo-copolymerization of an o-allenylaryl isocyanide. In the resulting polymer, the neighboring quinoline rings of the main chain form a layered structure with π–π interactions, which is stabilized by intramolecular hydrogen bonds. The vicinal quinoline units form two independent helices and the whole molecule is a twisted-tape structure. This structure is established on the basis of UV/CD spectra, theoretical calculations, and atomic-force microscopy.     

Construction of Helically Stacked π‐Electron Systems in Poly(quinolylene‐2,3‐methylene) Stabilized by Intramolecular Hydrogen Bonds

π‐Stacked polymers, which consist of layered π‐electron systems in a polymer, can be expected to be used in molecular electronic devices. However, the construction of a stable π‐stacked structure in a polymer is considerably challenging because it requires sophisticated designs and precise synthetic methods. Herein, we present a novel π‐stacked architecture based on poly(quinolylene‐2,3‐methylene) bearing alanine derivatives as the side chain, obtained through the living cyclo‐copolymerization of an o‐allenylaryl isocyanide. In the resulting polymer, the neighboring quinoline rings of the main chain form a layered structure with π–π interactions, which is stabilized by intramolecular hydrogen bonds. The vicinal quinoline units form two independent helices and the whole molecule is a twisted‐tape structure. This structure is established on the basis of UV/CD spectra, theoretical calculations, and atomic‐force microscopy.     

A hydrogel with rubber elasticity transition

Reaction between dimethyldivinylsilane and 3,6-diazaoctane in the presence of 3-lithio-3,6-diazaoctane yields a new telechelic oligomer, poly(silamine), which consists of alternating 3,3-dimethyl-3-silapentane and N,N′-diethylethylenediamine units in the main chain. Poly(silamine) shows unique phase transition properties in response to the degree of protonation of amino groups in the polymer. Poly(silamine) also shows a strong interaction with several anions. Due to the interaction between poly(silamine) and anions along with the protonation of amino groups in the poly(silamine), the rubber elasticity of poly(silamine) is drastically changed. A discrete volume change can be observed when the environmental pH of the poly(silamine) gels is varied. This can be explained not only by a change in ionic osmotic pressure but also by a change in the rubber elasticity of the networks in the gel.