Dioxygenases, key enzymes to determine the aglycon structures of fusicoccin and brassicicene, diterpene compounds produced by fungi

Fusicoccin A and cotylenin A are structurally related diterpene glucosides and show a phytohormone-like activity. However, only cotylenin A induces the differentiation of human myeloid leukemia cells. Since the cotylenin A producer lost its ability to proliferate during preservation, a study on the relationship between structure and activity was carried out and a modified fusicoccin A with hydroxyl group at the 3-position showed a similar biological activity with that of cotylenin A. We then searched for an enzyme source that catalyzes the introduction of a hydroxyl group into the 3-position and found that brassicicene C, which is structurally related to fusicoccin A with hydroxyl group at the 3-position, was produced by Alternaria brassicicola ATCC96836. We recently cloned a brassicicene C biosynthetic gene cluster including the genes encoding fusicocca-2,10(14)-diene synthase and two cytochrome P450s, which were responsible for the formation of fusicocca-2,10(14)-diene-8β,16-diol. In this study, we report that a α-ketoglutarate dependent dioxygenase, the gene coding for which was located in the cluster, catalyzed a hydroxylation at the 3-position of fusicocca-2,10(14)-diene-8β,16-diol. On the other hand, a α-ketoglutarate-dependent dioxygenase, which had been identified in a fusicoccin A biosynthetic gene cluster, catalyzed the 16-oxidation of fusicocca-2,10(14)-diene-8β,16-diol to yield an aldehyde (8β-hydroxyfusicocca-1,10(14)-dien-16-al), although both dioxygenases had 51% amino acid sequence identity. These findings suggested that the dioxygenases played critical roles for the formation of the fusicoccin A-type and cotylenin A-/brassicicene C-type aglycons. Moreover, we showed that short-chain dehydrogenase/reductase located in the fusicoccin A biosynthetic gene cluster catalyzed the reduction of the aldehyde to yield fusicocca-1,10(14)-diene-8β,16-diol.     

Ferroelectric Coordination Polymers Self‐Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands

A new class of ferroelectric coordination‐based polymers has been developed by the self‐assembly of lipophilic zinc porphyrin ( ZnP ) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination‐based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization–electric field (P–E) loops and inversion current peaks in current–voltage (I–V) loops. The observed ferroelectric properties are explainable by flip–flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive‐up–negative‐down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.     

Conjugates of stimuli-responsive polymers and biomolecules: Random and site-specific conjugates of temperature-sensitive polymers and proteins

Intelligent polymers exhibit sharp, reversible phase changes in response to small changes in environmental conditions. For example, a small temperature change can cause a sharp precipitation or gelation of a smart polymer solution. Conjugation of these unusual polymers to biomolecules such as enzymes, ligands, lipids, and drugs can lead to many new and exciting applications in medicine and biotechnology. (1–4) This presentation reviews the principles, methodolgies and applications of these “smart” polymer-biomolecule systems, with special focus on temperature-sensitive polymer-protein conjugates.     

On progressively truncated maximum likelihood estimators

Summary The basic regularity conditions pertaining to the asymptotic theory of progressively truncated likelihood functions and maximum likelihood estimators are considered, and the uniform strong consistency and weak convergence of progressively truncated maximum likelihood estimators are studied systematically. Work done during the first author's visit (as a visiting scholar) to the University of North Carolina at Chapel Hill, supported by the Ministry of Education of the Japanese Government. Work supported by the (U.S.) National Heart, Lung and Blood Institute, Contact NIH-NHLBI-F1-2243-L.     

Dense orbits of automorphisms and compactness of groups

It is proved, by using topological properties, that when a group automorphism of a locally compact totally disconnected group is ergodic under the Haar measure, the group is compact. The result is an answer for Halmos's question that has remained open for the totally disconnected case.     

Convergence Properties of the Regularized Newton Method for the Unconstrained Nonconvex Optimization

The regularized Newton method (RNM) is one of the efficient solution methods for the unconstrained convex optimization. It is well-known that the RNM has good convergence properties as compared to the steepest descent method and the pure Newton’s method. For example, Li, Fukushima, Qi and Yamashita showed that the RNM has a quadratic rate of convergence under the local error bound condition. Recently, Polyak showed that the global complexity bound of the RNM, which is the first iteration k such that ‖∇ f(x _k )‖≤ε, is O(ε ⁻⁴), where f is the objective function and ε is a given positive constant. In this paper, we consider a RNM extended to the unconstrained “nonconvex” optimization. We show that the extended RNM (E-RNM) has the following properties. (a) The E-RNM has a global convergence property under appropriate conditions. (b) The global complexity bound of the E-RNM is O(ε ⁻²) if ∇ ² f is Lipschitz continuous on a certain compact set. (c) The E-RNM has a superlinear rate of convergence under the local error bound condition.     

A large deviation principle for (r,p)-capacities on the Wiener space

Summary We formulate and prove a large deviation principle for the (r, p)-capacity on an abstract Wiener space. As an application, we obtain a sharpening of Strassen's law of the iterated logarithm in terms of the capacity.     

Fabrication and optical reflection behavior of a two-dimensional barium titanate ceramic photonic crystal

We demonstrate a method for fabricating a two-dimensional hexagonal array of nanoscale barium titanate ceramic pillars. A precursor array was prepared by introducing a sol solution into an electron-beam resist mold with air holes and subsequently dry etching the unnecessary gel layer formed on the mold. A ceramic array, consisting of barium titanate ceramic pillars with a radius of 85 nm, a lattice constant of 450 nm, and a height of 500 nm, was fabricated by sintering the precursor array at 1073 K. The reflection spectra for the ceramic array in the visible range revealed the underlying photonic band gaps, which were in good agreement with results calculated using a plane-wave method. PACS 77.84.-s; 42.70.-a; 42.70.Qs