A two-step approach to achieve secondary amide transamidation enabled by nickel catalysis.

A long-standing challenge in synthetic chemistry is the development of the transamidation reaction. This process, which involves the conversion of one amide to another, is typically plagued by unfavourable kinetic and thermodynamic factors. Although some advances have been made with regard to the transamidation of primary amide substrates, secondary amide transamidation has remained elusive. Here we present a simple two-step approach that allows for the elusive overall transformation to take place using non-precious metal catalysis. The methodology proceeds under exceptionally mild reaction conditions and is tolerant of amino-acid-derived nucleophiles. In addition to overcoming the classic problem of secondary amide transamidation, our studies expand the growing repertoire of new transformations mediated by base metal catalysis

Cyclin dependent kinase 1-dependent activation of APC/C ubiquitin ligase

Error-free genome duplication and segregation are ensured through the timely activation of ubiquitylation enzymes. The anaphase-promoting complex/cyclosome (APC/C), a multisubunit E3 ubiquitin ligase, is regulated by phosphorylation. However the mechanism remains elusive. Using systematic reconstitution and analysis of vertebrate APC/Cs under physiological conditions, we show how cyclin-dependent kinase 1 (CDK1) activates the APC/C through coordinated phosphorylation between Apc3 and Apc1. Phosphorylation of the loop domains by p9/Cks2 (CDK regulatory subunit)-CDK1 controlled loading of coactivator Cdc20 onto APC/C. A phosphomimetic mutation introduced into Apc1 allowed Cdc20 to increase APC/C activity in interphase. These results define a previously unrecognised subunit-subunit communication over a distance and the functional consequences of CDK phosphorylation. Cdc20 is a potential therapeutic target and our findings may facilitate the development of specific inhibitors

Anisotropic magnetic field responses of ferroelectric polarization in a trigonal multiferroic CuFe1-xAlxO2 (x=0.015)

We have investigated magnetic field dependences of a ferroelectric incommensurate-helimagnetic order in a trigonal magneto-electric (ME) multiferroic CuFe1-xAlxO2 with x=0.015, which exhibits the ferroelectric phase as a ground state, by means of neutron diffraction, magnetization and dielectric polarization measurements under magnetic fields applied along various directions. From the present results, we have established the H-T magnetic phase diagrams for the three principal directions of magnetic fields; (i) parallel to the c axis, (ii) parallel to the helical axis, and (iii) perpendicular to the c and the helical axes. While the previous dielectric polarization (P) measurements on CuFe1-xGaxO2 with x=0.035 have demonstrated that the magnetic field dependence of the `magnetic domain structure' results in distinct magnetic field responses of P [S. Seki et al., Phys. Rev. Lett., 103 237601 (2009)], the present study have revealed that the anisotropic magnetic field dependence of the ferroelectric helimagnetic order `in each magnetic domain' can be also a source of a variety of magnetic field responses of P in CuFe1-xAxO2 systems (A=Al, Ga).Comment: 11 pages, 9 figures, accepted for publication in Phys. Rev.

Development of a New Type Personal Dosemeter with Silicon Detector

開始ページ、終了ページ: 冊子体のページ付

Time scales and modes of reef lagoon infilling in the Maldives and controls on the onset of reef island formation

Faro are annular reefs, with reef flats near sea level and lagoons of variable depth, characteristic of both the perimeter and lagoons of Maldivian (Indian Ocean) atolls. Their geomorphic development remains largely unknown, but where faro lagoons (termed velu in Maldivian) have infilled and support reef islands, these provide precious habitable land. Understanding the timing and modes of velu infilling is thus directly relevant to questions about reef island development and vulnerability. Here we use a chronostratigraphic data set obtained from a range of atoll-interior faro with partially to fully filled velu (including those with reef islands) from Baa (South Maalhosmadulu) Atoll, Maldives, to determine time scales and modes of velu infilling, and to identify the temporal and spatial thresholds that control reef island formation. Our data suggest a systematic relationship between faro size, velu infilling, and island development. These relationships likely vary between atolls as a function of atoll lagoon depth, but in Baa Atoll, our data set indicates the following faro-size relationships exist: (1) faros <∼0.5 km2 have velu that were completely infilled by ca. 3000 calibrated years B.P. (cal yr B.P.) with islands having established on these deposits by ca. 2.5 cal kyr B.P.; (2) faros >0.5 km2 but <∼1.25 km2 have velu in late stages of infill, may support unvegetated sand cays and, given sufficient sand supply, may evolve into larger, more permanent islands; and (3) faros >∼1.25 km2 have unfilled (deeper) velu which might only infill over long time scales and which are thus unlikely to support new island initiation. These new observations, when combined with previously published data on Maldivian reef island development, suggest that while the velu of the largest faro are unlikely to fill over the next few centuries (at least), other faro with near-infilled velu may provide important foci for future reef-island building, even under present highstand (and slightly rising) sea levels

Interplay between Phosphatases and the Anaphase-Promoting Complex/Cyclosome in Mitosis

Accurate division of cells into two daughters is a process that is vital to propagation of life. Protein phosphorylation and selective degradation have emerged as two important mechanisms safeguarding the delicate choreography of mitosis. Protein phosphatases catalyze dephosphorylation of thousands of sites on proteins, steering the cells through establishment of the mitotic phase and exit from it. A large E3 ubiquitin ligase, the anaphase-promoting complex/cyclosome (APC/C) becomes active during latter stages of mitosis through G1 and marks hundreds of proteins for destruction. Recent studies have revealed the complex interregulation between these two classes of enzymes. In this review, we highlight the direct and indirect mechanisms by which phosphatases and the APC/C mutually influence each other to ensure accurate spatiotemporal and orderly progression through mitosis, with a particular focus on recent insights and conceptual advances

Thyroid hormone receptor expression during metamorphosis of Atlantic halibut (Hippoglossus hippoglossus)

Flatfish such as the Atlantic halibut (Hippoglossus hippoglossus) undergo a dramatic metamorphosis that transforms the pelagic, symmetric larva into a benthic, cranially asymmetric juvenile. In common with amphibian metamorphosis, flatfish metamorphosis is under endocrine control with thyroid hormones being particularly important. In this report we confirm that tri-iodothyronine (T3) levels peak at metamorphic climax during halibut metamorphosis. Moreover we have isolated cDNA clones of TR and TR genes and confirmed the presence in halibut of two TR isoforms (representing the products of distinct genes) and two TR isoforms (generated from a single gene by alternative splicing). Real time PCR was used to assess expression of these genes during metamorphosis. TR shows the most dramatic expression profile, with a peak occurring during metamorphic climax.This work has been carried out within the project “Arrested development: The Molecular and Endocrine Basis of Flatfish Metamorphosis” (Q5RS-2002-01192) with financial support from the Commission of the European Communities. However, it does not necessarily reflect the Commission’s views and in no way anticipates its future policy in this area. We thank Heiddis Smáradóttir (Fiskeldi Eyjafjarðar, IS-600 Akureyri, Iceland) for collecting and providing the Atlantic halibut samples, and Karin Pittman and Øystein Sæle (both from the Department of Biology, University of Bergen, Norway) for analysing samples to determine developmental stage. We are also grateful to Marco Campinho for preparing the RNA used in the study