Bidentate amidine ligands for nickel(0)-mediated coupling of carbon dioxide with unsaturated hydrocarbons

Novel bidentate amidines were designed and synthesized as easily available electron-donating N-ligands for Ni0-mediated coupling of carbon dioxide with alkynes or allenes, and high regioselectivity was achieved even for the carboxylation of aryl substituted internal alkynes.     

Rhodium‐Catalyzed C−H Activation Enabled by an Indium Metalloligand

Rhodium complexes with an indium metalloligand were successfully synthesized by utilizing a pyridine‐tethered cyclopentadienyl ligand as a support for an In?Rh bond. The indium metalloligand dramatically changes the electronic and redox properties of the rhodium metal, thereby enabling catalysis of sp²C?H bond activation.     

Dynamic Interconversion between Boroxine Cages Based on Pyridine Ligation

Dynamic interconversion between large covalent organic cages was achieved simply by heating or acid/base treatment. A mixture of the boroxine cages 12‐mer and 15‐mer was cleanly converted into a pyridine adduct of the 9‐mer boroxine cage upon treatment with pyridine, and the geometry of N‐coordinated boron atoms changed from trigonal to tetrahedral. The reverse reaction was achieved by heating or acid treatment. In this process, the larger boroxine cages 12‐mer and 15‐mer were found to be entropically favored owing to the release of free pyridine molecules from 9‐mer ?6 Py.     

Real-time observation of coadsorption layers on Ru(001) using a temperature-programmed ESDIAD/TOF system

For the purpose of utilizing ESDIAD as a real-time probe for surface processes, we have developed an instrument which can measure ESDIAD images and time of flight (TOF) spectra of desorbing ions in temperature-programmed surface processes. TOF measurements are carried out to identify the mass and to determine the kinetic energy distribution of the desorbed ions. This temperature-programmed (TP-) ESDIAD/TOF system was used to observe coadsorption layers of methylamine and CO on Ru(001) which have been previously studied by our group using LEED, TPD and HREELS, also drawing upon a comparison of findings with the coadsorption system of CO and ammonia. ESDIAD images acquired for temperature-programmed surface processes in real time were found to provide new insight into the dynamic behaviour of the coadsorption layers. As to the pure adsorption of ammonia and methylamine, the second and the first (chemisorbed) layers can be easily discriminated in their different ESD detection efficiency due to the difference in neutralization rate. The intensity change of H⁺ ions with temperature shows the process of the decomposition of methylamine to be dependent on CO coverage. The intensity of O⁺ originating from CO changes due to the change of CO adsorption site in the reaction process. The angular distribution of H⁺ ions which correspond to CH2=NH…Ru species appears at 250–300 K in the presence of high CO pre-coverage.     

Straightforward access to functionalized pentaarylbenzene derivatives through a quick lithiation

A straightforward route to functionalized pentaarylbenzene derivatives is described, involving the effective lithiation method of 1-iodo-2,3,4,5,6-pentaarylbenzene. The activated pentaarylbenzene is a potential synton for producing organic materials.     

Photoreactivation in Paramecium tetraurelia under conditions of various degrees of ozone layer depletion

Photoreactivation (PR) is an efficient survival mechanism that helps protect cells against the harmful effects of solar-ultraviolet (UV) radiation. The PR mechanism involves photolyase, just one enzyme, and can repair DNA damage, such as cyclobutane-pyrimidine dimers (CPD) induced by near-UV/blue light, a component of sunlight. Although the balance of near-UV/blue light and far-UV light reaching the Earth's surface could be altered by the atmospheric ozone layer's depletion, experiments simulating this environmental change and its possible effects on life have not yet been performed. To quantify the strength of UVB in sunlight reaching the Earth's surface, we measured the number of CPD generated in plasmid DNA after UVB irradiation or exposure to sunlight. To simulate the increase of solar-UV radiation resulting from the ozone layer depletion, Paramecium tetraurelia was exposed to UVB and/or sunlight in clear summer weather. PR recovery after exposure to sunlight was complete at a low dose rate of 0.2 J/m2 x s, but was less efficient when the dose rate was increased by a factor of 2.5 to 0.5 J/m2 x s. It is suggested that solar-UV radiation would not influence the cell growth of P. tetraurelia for the reason of high PR activity even when the ozone concentration was decreased 30% from the present levels.