Publications by authors named "Totani R"

By exciting a series of 1s^{2} ^{1}S_{0}→1snp^{1}P_{1} transitions in heliumlike nitrogen ions with linearly polarized monochromatic soft x rays at the Elettra facility, we found a change in the angular distribution of the fluorescence sensitive to the principal quantum number n. In particular it is observed that the ratio of emission in directions parallel and perpendicular to the polarization of incident radiation increases with higher n. We find this n dependence to be a manifestation of the Hanle effect, which served as a practical tool for lifetime determinations of optical transitions since its discovery in 1924.

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The valence and core photoelectron spectra of three substituted disulfide systems, α-lipoic acid, trans-4,5-dihydroxy-1,2-dithiane, and di-Boc-cystamine, are presented alongside detailed theoretical analysis based on equation-of-motion coupled-cluster singles doubles for ionization potentials and the nuclear ensemble approach. A comparison of the linear and five- and six-membered ring cyclic structures reveals that the energetic separation of the non-bonding sulfur orbitals can be used to calculate a reliable estimate of the C-S-S-C dihedral angle, even for substituted disulfides, and that the sulfur 2p, oxygen 1s, and valence band photoelectron spectra are a useful site-specific probe of hydrogen bonding.

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We have measured, analyzed, and simulated the ground state valence photoelectron spectrum, x-ray absorption (XA) spectrum, x-ray photoelectron (XP) spectrum as well as normal and resonant Auger-Meitner electron (AE) spectrum of oxazole at the carbon, oxygen, and nitrogen K-edge in order to understand its electronic structure. Experimental data are compared to theoretical calculations performed at the coupled cluster, restricted active space perturbation theory to second-order and time-dependent density functional levels of theory. We demonstrate (1) that both N and O K-edge XA spectra are sensitive to the amount of dynamical electron correlation included in the theoretical description and (2) that for a complete description of XP spectra, additional orbital correlation and orbital relaxation effects need to be considered.

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Purpose: In living organisms, sensitivity to radiation increases in the presence of oxygen (O) compared with that under anoxic or hypoxic conditions. Here, we investigated whether O concentration affected the response of mitochondria to X-rays radiation, which is associated with tumor microenvironment formation via fibroblast activation in radiation-related tumors.

Materials And Methods: O concentrations were controlled at <5% (internal environmental oxygen condition) or anoxic levels during culture of normal human diploid lung fibroblasts TIG-3 and MRC-5.

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The electronic characterization of the cyanuric acid both in gas phase and when embedded within an H-bonded scheme forming a monolayer on the Au(111) surface has been performed by means of X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The experimental spectra at the N, O, and C -edges have been assigned with the support of DFT calculations, and the combination between theory and experiment has allowed to us investigate the effect of the H-bonding intermolecular interaction on the spectra. In particular, the H-bond formation in the monolayer leads to a quenching of the N 1s NEXAFS resonances associated with transitions to the sigma empty orbitals localized on the N-H portion of the imide group.

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We have investigated the frontier orbitals of persistent organic radicals known as nitroxyls by resonant photoelectron spectroscopy (ResPES) under inner shell excitation. By means of this site-specific technique, we were able to disentangle the different atomic contributions to the outer valence molecular orbitals and examine several core-hole relaxation pathways involving the singly occupied molecular orbital (SOMO) localized on the nitroxyl group. To interpret the ResPES intensity trends, especially the strong enhancement of the SOMO ionized state at the N K-edge, we computed the Dyson spin orbitals (DSOs) pertaining to the transitions between the core-excited initial states and several of the singly ionized valence final states.

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The electronic properties of a diboron molecule, namely bis(catecholato)diboron (2-(1,3,2-benzodioxaborol-2-yl)-1,3,2-benzodioxaborole) (BCat), have been studied by comparing the results of photoemission (XPS) and near edge X-ray absorption spectroscopy (NEXAFS) experiments with the outcome of DFT calculations. The B 1s, C 1s and O 1s K-edges have been investigated for both the isolated gas phase molecule and the adsorbed one on the Au(111) surface. The main features of the polarized NEXAFS spectra at each of the three edges considered are not significantly affected by the presence of the substrate, with respect to the isolated molecule, indicating that the molecule-gold interaction is weak.

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Aims: A number of epidemiologic surveys have demonstrated that improving lifestyle habits, providing patient education, and regular screening of patients for early diabetic symptoms and complications through multidisciplinary collaboration are crucial for the management of diabetes.

Methods: To evaluate the Diabetes Coordination Notebook and the Diabetes Regional Coordination Path in management of diabetes, 217 community pharmacies conducted a survey by questionnaire in Gifu Prefecture, Japan.

Results: A reply to the questionnaire was obtained from 27,016 individuals, of whom 5,572 claimed to have diabetes or prediabetes.

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Aims: A questionnaire survey of the prevalence of diabetic retinopathy was recently conducted in Japan. A subgroup analysis to examine the association of periodontal disease with diabetic retinopathy in subjects with diabetes and prediabetes was conducted.

Methods: The association of the presence of periodontal disease with the occurrence of diabetic retinopathy was examined using multivariate logistic regression analysis.

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Photoelectron Spectroscopy (PS) and Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy have been used to investigate the occupied and empty density of states of biphenylene films of different thicknesses, deposited onto a Cu(111) crystal. The obtained results have been compared to previous gas phase spectra and single molecule Density Functional Theory (DFT) calculations to get insights into the possible modification of the molecular electronic structure in the film induced by the adsorption on a surface. Furthermore, NEXAFS measurements allowed characterizing the variation of the molecular arrangement with the film thickness and helped to clarify the substrate-molecule interaction.

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In this paper, we provide detailed insights into the electronic structure of the gas phase biphenylene molecule through core and valence spectroscopy. By comparing results of X-ray Photoelectron Spectroscopy (XPS) measurements with ΔSCF core-hole calculations in the framework of Density Functional Theory (DFT), we could decompose the characteristic contributions to the total spectra and assign them to non-equivalent carbon atoms. As a difference with similar molecules like biphenyl and naphthalene, an influence of the localized orbitals on the relative XPS shifts was found.

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To shed light on the metal 3d electronic structure of manganese phthalocyanine, so far controversial, we performed photoelectron measurements both in the gas phase and as thin film. With the purpose of explaining the experimental results,three different electronic configurations close in energy to one another were studied by means of density functional theory. The comparison between the calculated valence band density of states and the measured spectra revealed that in the gas phase the molecules exhibit a mixed electronic configuration, while in the thin film, manganese phthalocyanine finds itself in the theoretically computed ground state, namely, the b1(2g)e3(g)a1(1g)b0(1g) electronic configuration.

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We collected blood samples from 70 HIV-1-infected pregnant women and 76 babies born to HIV-1-infected women in Japan, from 1989 to 1999. To analyze the genetic diversity of HIV-1 among mothers and children, we sequenced the C2-V3 regions of HIV-1 gp120. Phylogenetic tree analysis of these regions revealed that multiple HIV-1 subtypes, A, B, D, E, and G, were circulating among mothers and children in Japan.

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The prevalence of diabetic ocular complications and the correlation between diabetic retinopathy and systemic factors were examined in 2,300 cases (4,600 eyes) with non-insulin-dependent diabetes mellitus. The prevalence of cataract was 66.7%, of retinopathy 37.

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The purpose of this study was to test the validity of our working hypothesis that the stress of radical surgery may affect the prognosis of a cancer patient by precipitating hematogenous tumor metastasis, and that enhancement of this type of tumor metastasis is mediated by an increase of glucocorticoid activity that is induced in a cancer patient by surgical stress. Practically, we looked for the presence of glucocorticosteroid excess in cervical cancer patients in the course of radical surgery, and also tested the possible impact of glucocorticoid excess on the development of tumor metastasis in mice with i.v.

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We compared the hormonal and epidemiological aspects of ovarian cancer patients in search of the etiology of this neoplasia. Case-control studies of Japanese women with and without cancer were conducted in parallel, with regard to both the excretion of 14 urinary steroids and the pertinent physical and physiological parameters. The results obtained are as follows: 1) premenopausal ovarian cancer patients before and after radical ovariectomy and postmenopausal-postoperative patients were associated with a specified steroid deviation profile characterized by a combination of general depression of androgens, progestins and corticosteroids with sole rescue of tetrahydrocortisol (THF) in urine.

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Chronological trend of urinary steroid excretions in Japanese women was investigated during the period of June 1972 to August 1986 using healthy women of urban and rural origins, patients with breast cancer and patients with either cervical cancer or endometrial cancer. The excretions of 14 neutral steroids were estimated by gas liquid chromatography, and the obtained data were tentatively correlated with the epidemiological backgrounds. In the course of the chronological transition from the 1st stage (1972-1974) to the 2nd stage (1975-79), the urinary steroid pattern of Japanese women with and without cancer experienced a common change to produce specific deviations that were in agreement with the hormonal characteristics of a pill user or of an endometrial cancer patient.

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The relation between 14 urinary steroid excretions was investigated by intersteroidal regression analysis with urine from 59 follicular stage women, 135 luteal stage women and 5 female patients with adrenal disorders. The regularity of intersteroidal relation in urine, as detected for all steroid pairs of all groups studied, was explained in terms of the law of mass action, and a chemical equilibrium point was located with a high degree of reproducibility for each steroid and for each group. The theoretical and practical usefulness of urinary steroid regression analysis is emphasized in relation to the possible impact of multihormonal information on endocrinology.

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ACTH responses to corticotropin-releasing hormone (CRH) were studied in three patients with the ectopic ACTH syndrome caused by lung cancer. Plasma ACTH responded to synthetic CRH in two of three patients. Tumor tissues obtained from these two patients contained CRH and ACTH.

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We performed a case-control study to investigate the urinary steroid excretions in ovarian cancer patients. The use of gas-liquid chromatography permitted the estimation of 14 urinary steroids. Data on 139 urine specimens from 36 cancer patients were compared with those on age-matched controls.

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To achieve maximum dilatation of the Fallopian tubes so as to improve the pregnancy: non-pregnancy ratio of hysterosalpingography (HSG) treatment, a high-pressure injection technique was evaluated. For this purpose a disposable cannula and an adapted pair of tenacula were developed and a remote-control procedure using an auto-injector and an adapted pressure recorder was used to assure the safety of doctors and staff. 1780 cases who underwent 400 mmHg high-pressure HSG treatment were compared with 903 conventional HSG cases.

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