A theoretical study on the third-order nonlinear optical properties of pi-conjugated linear porphyrin arrays

By using the Pariser-Parr-Pople (PPP) theory, the second hyperpolarizabilities (gamma) have been calculated for various pi-conjugated porphyrin arrays including "porphyrin tapes": the meso-beta doubly linked porphyrin array Dn and the meso-meso, beta-beta, beta-beta triply linked array Tn. The validity of the PPP theory is checked via a comparison with both the ab initio Hartree-Fock and the B3LYP theories in the case of porphyrin monomers and dimers. It is found that Dn and especially Tn exhibit much more remarkable evolution of gamma/n along with an increasing number of porphyrin units n compared with the butadiyne-bridged array, Yn. As a result, the static third-order susceptibilities chi((3)) of Dn and Tn are expected to be 1 and 3 orders of magnitude larger than that of Yn in the limit n --> infinity, and these advantages of porphyrin tapes become more prominent by taking into account geometrical relaxations of porphyrin units in the arrays. The structure-property relationship in various conjugated polymers including porphyrin arrays is interpreted on the basis of the scaling behaviors of chi((1)) and chi((3)) with the effective conjugation length (ECL) as well as the reciprocal HOMO-LUMO energy gap (1/E(g)). In particular, from the master plot of chi((3)) (and even chi((1))) versus 1/E(g), the pi-conjugation of Tn is noted to indeed be exceptional, because its large susceptibilities cannot be expected from the scaling behavior of ordinary one-dimensional conjugated systems. We also point out that the theory of scaling relationship, chi((3)) approximately 1/E(g)(x)(), is significantly improved by taking into account electron-electron interactions based on the comparison with experiments.     

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.     

Molecular biology of histidine decarboxylase and prostaglandin receptors

Histamine and prostaglandins (PGs) play a variety of physiological roles as autacoids, which function in the vicinity of their sources and maintain local homeostasis in the body. They stimulate target cells by acting on their specific receptors, which are coupled to trimeric G proteins. For the precise understanding of the physiological roles of histamine and PGs, it is necessary to clarify the molecular mechanisms involved in their synthesis as well as their receptor-mediated responses. We cloned the cDNAs for mouse L-histidine decarboxylase (HDC) and 6 mouse prostanoid receptors (4 PGE(2) receptors, PGF receptor, and PGI receptor). We then characterized the expression patterns and functions of these genes. Furthermore, we established gene-targeted mouse strains for HDC and PG receptors to explore the novel pathophysiological roles of histamine and PGs. We have here summarized our research, which should contribute to progress in the molecular biology of HDC and PG receptors.     

Recent insights into iron homeostasis and their application in graminaceous crops

Higher plants utilize various mechanisms to maintain iron homeostasis. To acquire sparingly soluble iron from the rhizosphere, graminaceous plants synthesize natural iron (III) chelators known as mugineic acid family phytosiderophores (MAs). Recent research has uncovered various genes involved in iron uptake and translocation, as well as factors regulating the expression of these genes, especially in rice. Manipulation of these molecular components is used to produce transgenic crops with enhanced tolerance to iron deficiency, or with a high seed iron content. Since iron homeostasis is closely linked to that of other mineral elements, an understanding of this phenomenon will serve as the basis for the production of crops with low concentrations of toxic metals and transgenic plants for phytoremediation.