Theoretical and experimental investigation on the electronic properties of the shuttlecock shaped and the double-decker structured metal phthalocyanines, MPc and M(Pc)2 (M = Sn and Pb).

The molecular geometries, electronic structures, and excitation energies of tin and lead phthalocyanine compounds, SnPc, PbPc, Sn(Pc)(2), and Pb(Pc)(2), were investigated using the B3LYP method within a framework of density functional theory (DFT). The geometries of SnPc, PbPc, Sn(Pc)(2), and Pb(Pc)(2) were optimized under C(4v), C(4v), D(4d), and D(4d) molecular symmetries, respectively. The excitation energies of these molecules were computed by the time-dependent DFT (TD-DFT) method. The calculated results for the excited states of three compounds other than the unknown Pb(Pc)(2) corresponded well with the experimental results of electronic absorption spectroscopy. The non-planar C(4v) molecular structure of SnPc and PbPc influences especially on the orbital energy of the HOMO-1 through mixing of the s-type atomic orbital of the central metal atom to the π system of the Pc ring in an anti-bonding way; however, the HOMO and the LUMO have little effect of the deviation from the planar structure because they have no contribution from the atomic orbital of the central metal. This orbital mixing pushes up the orbital energy of the HOMO-1, and reduces the energy of the metal-to-ligand charge transfer band of SnPc and PbPc. The calculated results also reproduced well the excitation profile of Sn(Pc)(2), which was quite different from that of SnPc. The strong interactions between the π-type orbitals of two Pc moieties altered the electronic structure resulting in the characteristic excitation profile of Sn(Pc)(2). In addition, this caused a reduction of about 0.8 eV in the ionization potential as compared to usual MPcs including SnPc, which was consistent with the experimental results.

Autochthonous experience, heightened awareness, and perception distortion in patients with schizophrenia: a symptomatological study.

Early symptoms of schizophrenia' (ESS) proposed by Nakayasu, are present during schizophrenic prodromal periods. Some of these symptoms can continue after the florid manifestation of the disease and the patients often experience them with ego-alien feelings. Autochthonous experience, heightened awareness, and perception distortion (AHP) were selected from the list of ESS. The aim of this study was to confirm both prevalence and specificity of AHP in patients with schizophrenia as well as the relevance of the presence of AHP to symptomatology of schizophrenia. A structured interview was conducted to identify the presence of AHP in three groups of subjects; a schizophrenia group (Sc) with 37 patients, an affective disorder group (AD) with 27 patients, and a control group (NC) with 39 people. The prevalence of AHP was compared among the groups. Within the Sc, the relevance of AHP to Brief Psychiatric Rating Scale (BPRS) was assessed. AHP were present significantly more frequently in the Sc. The total scores for BPRS in the schizophrenic patients with AHP were significantly higher than in the patients without AHP. There was close correlation between AHP and BPRS items, with the degree of relevance depending on the form or perceptual domain. In conclusion, AHP were characteristic of patients with frank schizophrenia. To judge whether AHP were adequately specific to frank schizophrenia, further research of larger subjects is needed. Understanding the characteristics of AHP in patients with frank schizophrenia is important in the symptomatological evaluation of schizophrenia.

Spatial distribution of 3H, 90Sr, 137Cs and (239,240)Pu in surface waters of the Pacific and Indian Oceans--GLOMARD database.

The data stored in the IAEA's Global Marine Radioactivity Database (GLOMARD) developed in the framework of the IAEA's project "Worldwide Marine Radioactivity Studies (WOMARS)" have been evaluated for Pacific and Indian Ocean surface waters. Four anthropogenic radionuclides-- 3H, 90Sr, 137Cs and (239,240)Pu --have been chosen as the most representative of anthropogenic radioactivity in the marine environment, comprising beta, gamma and alpha-emitters which are the most frequently analysed in the marine environment and which have (with the exception of tritium) the highest potential contribution to radiation doses to humans via seafood consumption. For the purposes of this study, the Pacific and Indian Oceans were divided into latitudinal boxes for which average radionuclide concentrations were estimated for the year 2000. The highest concentrations have been observed in the Japan Sea/East Sea and the North-West Pacific Ocean, the lowest in the Southern Ocean.