A dual-level state-specific time-dependent density-functional theory

A highly efficient new algorithm for time-dependent density-functional theory (TDDFT) calculations is presented. In this algorithm, a dual-level approach to speed up DFT calculations (Nakajima and Hirao, J Chem Phys 2006, 124, 184108) is combined with a state-specific (SS) algorithm for TDDFT (Chiba et al., Chem Phys Lett 2006, 420, 391). The dual-level SS-TDDFT algorithm was applied to excitation energy calculations of typical small molecules, the Q bands of the chlorophyll A molecule, the charge-transfer energy of the zincbacteriochlorin-bacteriochlorin model system, and the lowest-lying excitation of the circumcoronene molecule. As a result, it was found that the dual-level SS-TDDFT gave correct excitation energies with errors of 0.2-0.3 eV from the standard TDDFT approach, with much lower CPU times for various types of excitation energies of large-scale molecules.     

Use of laser drilling in the manufacture of organic inverter circuits

Inverter circuits have been made by connecting two high-quality pentacene field-effect transistors. A uniform and pinhole-free 900 nm thick polyimide gate-insulating layer was formed on a flexible polyimide film with gold gate electrodes and partially removed by using a CO₂ laser drilling machine to make via holes and contact holes. Subsequent evaporation of the gold layer results in good electrical connection with a gold gate layer underneath the gate-insulating layer. By optimization of the settings of the CO₂ laser drilling machine, contact resistance can be reduced to as low as 3 Ω for 180 μm square electrodes. No degradation of the transport properties of the organic transistors was observed after the laser-drilling process. This study demonstrates the feasibility of using the laser drilling process for implementation of organic transistors in integrated circuits on flexible polymer films.     

Regiocontrolled intramolecular cyclizations of carboxylic acids to carbon-carbon triple bonds promoted by acid or base catalyst

We systematically investigated, for the first time, the relationship between regioselectivity and acid/base effects in the cyclization reactions between carboxylic acids and carbon-carbon triple bonds. We found novel acid- and base-promoted cyclizations to selectively give isocoumarin or pyran-2(2H)-one and phthalide or furan-2(5H)-one skeletons, respectively, and established a catalytic version of regioselective heterocyclic ring synthesis. Density functional theory calculations and application to a short route to thunberginol A were also described. [reaction: see text].     

Theoretical study on molecular property of protactinium(V) and uranium(VI) oxocations: why does protactinium(V) form monooxo cations in aqueous solution?

The stability of Pa(V) and U(VI) oxocations in aqueous solution were theoretically investigated by means of density functional theory calculations. As a result, the present calculations clearly supported an experimental result from an energetic point of view that monooxo protactinyl cation, PaO3+, is a preferable species for Pa(V) in aqueous solution, although dioxo protactinyl cation, PaO2+, is not a feasible form. By an analysis of molecular orbitals, we revealed that 6d orbitals of Pa(V) destabilize the pi orbitals of PaO2+, because 6d-2p antibonding orbital conflicts with another 5f-2p bonding orbital. For stable dioxo uranyl cation, UO2(2+), we found that 6d orbitals of U(VI), in contrast, form a bonding orbital with the 2p orbitals, and this bonding orbital coexists at an angle with the 5f-2p bonding orbital due to an electron correlation.     

4-(Pyrrolidinyl)methoxybenzoic acid derivatives as a potent, orally active VLA-4 antagonist

A novel series of benzoic acid derivatives as VLA-4 antagonists were synthesized. Optimization, focusing on activity and lipophilicity needed for cell permeability, resulted in the identification of 15b and 15e with good activity (IC50 = 1.6 nM each) and moderate lipophilicity (Log D = 2.0, 1.8). Furthermore, 15e demonstrated efficacy in murine asthma model by an oral dose of 30 mg/kg.     

Bisbenzylisoquinoline Alkaloids from Nelumbo nucifera

From the embryos of the seeds of Nelumbo nucifera, three bisbenzylisoquinoline alkaloids, nelumboferine and nelumborines A and B, were isolated along with four known compounds, neferine, liensinine, isoliensinine and anisic acid. The structures of the new alkaloids were determined mainly by spectroscopic methods.