Potential-Dependent Adsorption and Orientation of meso-Substituted Porphyrins at Liquid|Liquid Interfaces Studied by Polarization-Modulation Total Internal Reflection Fluorescence Spectroscopy

Potential-dependent adsorption behavior of meso-substituted water-soluble porphyrins at the polarized water|1,2-dichloroethane (DCE) interface was studied by polarization-modulation total internal reflection fluorescence (PM-TIRF) spectroscopy. In the PM-TIRF experiments, the fluorescence signal from the interfacial region was analyzed as a function of the periodic modulation of linear-polarizations (p and s) of the incident excitation beam. The potential-dependence of PM-TIRF responses for meso-substituted porphyrins, 5,10,15,20-tetrakis(N-methylpyridyl)porphyrin (H2TMPyP4+) and 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4-), indicated that both free base porphyrins were adsorbed with relatively lying orientations at the polarized water|DCE interface. The average orientation angles (θ) were estimated as θ = 61 ± 1°for H2TMPyP4+ and θ = 65 ± 1°for H2TPPS4- with respect to the interface normal. The wavelength-dependence of polarization-modulated fluorescence signals (PM-TIRF spectrum), which corresponds to "pure" emission spectrum of interfacial species, clearly indicated that H2TMPyP4+ and H2TPPS4- are adsorbed with a modification of the solvation at the interface. These results demonstrated a high ability of the PM-TIRF spectroscopy for the direct characterization of fluorescent species adsorbed at polarized liquid|liquid interfaces. © 2016 American Chemical Society.Embargo Period 12 months / This article has Supplementary dat

Energy Dependence of the Line Ratio I(233.9 Å)/I(243.8 Å) in Fe xv Observed with an Electron Beam Ion Trap

We present the energy dependence of the intensity ratio between the 3s3p3P2—3s3d3D3 transition at 233.9 Å and the 3s3p1P1—3s3d1D2 transition at 243.8 Å in Fe xv studied with an electron beam ion trap over an energy range that spans resonance excitation regions. Clear resonance structures are observed in the electron energy range of 400–600 eV. The energy dependence obtained in the experiment is compared with a collisional-radiative model calculation, including resonance excitations, and overall agreement is found. It is shown that the ratio strongly reflects the population of the 3s3p3P2 metastable state, which is the lower state of the 233.9 Å transition

Potential-Induced Aggregation of Anionic Porphyrins at Liquid|Liquid Interfaces

金沢大学理工研究域物質化学系The adsorption and self-aggregation of anionic porphyrins were studied at the polarized water|1,2-dichloroethane (DCE) interface by polarization-modulation total internal reflection fluorescence (PM-TIRF) spectroscopy. 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin diacid (H4TPPS2-) and protoporphyrin IX (H2PP2-) exhibited high surface activities at the interface. The selective excitation of interfacial species in PM-TIRF measurements elucidated the potential-induced aggregation mechanism of the porphyrins. The J-aggregates of H4TPPS2- were reversibly formed only at the water|DCE interface by applying appropriate potentials even when the porphyrins exist as monomers in the aqueous and organic solutions. In the H2PP2- system, the slow aggregation process was found in the negative potential region. The spectral characteristics and the signal phase of PM-TIRF indicated that the H2PP2- monomers were adsorbed with relatively standing orientation and that the long axis of the J-aggregates was nearly in plane of the interface. H2PP2- was also investigated at the biomimetic phospholipid-adsorbed water|DCE interface. The competitive adsorption of neutral glycerophospholipids effectively inhibited the potential-dependent adsorption and interfacial aggregation processes of H2PP2-. The results demonstrated that the aggregation state of the charged species can reversibly be controlled at liquid|liquid interfaces as a function of externally applied potential. © 2017 American Chemical Society.Embargo Period 12 month

X-Ray Analysis Literatures 2012

2012年に出版されたX線分析に関連する文献および情報について，X線分析技術の発展に寄与し重要であると編集委員が選抜した文献を総説としてまとめた．調査対象はe-ジャーナル，webマガジンを含む学術誌18誌，制定された規格およびX線関連メーカーの新技術情報である．各雑誌について全体的な傾向および選抜したいくつかの論文に対して論評を記した．The selected literatures about advances in X-ray analysis and X-ray analysis-related information published in 2012 were reviewed on the basis of analytical chemistry, physics, techniques, optics, instrumentation and so forth. The 18 kinds of academic journals including web-magazines, Japanese Industrial Standard (JIS), and websites of companies related with X-ray tools and/or X-ray apparatus were researched. The trend of publications related to X-ray analysis for each journal was overviewed, and some of noticeable literatures were commented

THYROID DYSFUNCTION FOLLOWING ALPHA-INTERFERON TREATMENT FOR CHRONIC HEPATITIS C

In order to evaluate the influnces of IFNα on thyroid function, thyroid-stimulating hormone (TSH), total thyroxine (T4), free T4, tri-iodothyronine (T3), and thyroxine-binding globulin were examined in IFNα-treated 351 patients with chronic hepatitis C before and during therapy. As therapy, either 3 million units (MU) of human lymphoblastoid IFNα or 9MU of recombinant IFNα2a was administrated daily for the initial two weeks followed by three times a week for 22 weeks. There were nine patients showing thyroid dysfunction during IFNα therapy. They consist of one relapse of Graves' disease, one relapse of Hashimoto thyroiditis, one development of apparent thyroid insufficiency from subclinical hypothyroidism, five cases with transient hyperthyroidism and one case with transient hypothyroidism. T4 and T3 levels in most patients who transiently developed thyroid dysfunction were normalized spontaneously after the discontinuation of IFNα. Thyroid-related autoantibodies were positive in 4 patients before IFNα therapy and newly developed in one patient during therapy. Attention should be paid first to the previous histories of autoimmune thyroid diseases and the existence of thyroid-related autoantibodies for the prediction of development of thyroid dysfunction during IFNα therapy. In addition, serial examinations of TSH, T3 and T4 should be also necessary for early detection of transient thyroid dysfunction during IFNα therapy

Aggregation-Induced Emission of Water-Soluble Tetraphenylethene Derivatives at Polarized Liquid|Liquid Interfaces

金沢大学物質化学系Aggregation-induced emission (AIE) behavior of water-soluble tetraphenylethene (TPE) derivatives bearing carboxy and sulfo groups was studied at polarized liquid|liquid interfaces. The aggregation behavior of TPE derivatives in solution and at the water|1,2-dichloroethane (DCE) interface was highly dependent on their ionizable functional groups. Spectroelectrochemical analysis elucidated that the TPE derivatives were transferred across the interface accompanied by the adsorption process at the interface. The ion transfer and interfacial AIE features of TPEs responded reversibly to the externally applied potential, indicating no rigid crystalline structure formation in the interfacial region. The red shift measured in intense interfacial emission spectra demonstrated that the carboxylate derivatives formed their J-aggregates specifically at the polarized water|DCE interface, while the aggregation processes with distinguishable emission properties took place in both the interfacial region and organic solution in the sulfonate derivative system. The AIE features were also investigated at a glycerophospholipid-adsorbed interface as a model of the biomembrane surface. The aggregation process of TPE derivatives was significantly modified through the interaction with phospholipid layers which stimulate the interfacial AIE process of tetra-anionic TPEs.Embargo Period 12 monthsThis paper has a Supplementary material

X-Ray Analysis Literatures 2011

2011年に出版されたX線分析関連文献，X線に関連した情報のなかで，編集委員がX線分析技術の発展に寄与し重要であると選抜した文献を総説としてまとめた．調査対象はe-ジャーナル，web マガジンを含む学術誌20誌，制定された規格およびX線関連メーカーの新技術情報である．各雑誌について，全体的な論評，X線分析に関する傾向から，いくつかの論文について論評を記した．The selected literatures about advances in X-ray analysis and X-ray analysis-related informations published in 2011 were reviewed on the basis of analytical chemistry, physics, techniques, optics, instrumentation and so forth. The 20 kinds of academic journals including web-magagines, Japanease Industrial Standard (JIS), and websites of companies related with X-ray tools and/or X-ray apparatus were researched. The trend of publications related to X-ray analysis for each journal was overviewed, and some of noticeable literatures were commented

X-Ray Analysis Literatures 2010

本総説は，2010年に学術雑誌に掲載されたX線分析関連の論文において，注目すべき論文を厳選し紹介する．調査した学術雑誌は19件（和雑誌2件含む）であり，X線分析の発展に寄与しているものを対象としているが，分析化学の分野だけでなく，分光学や物理学の分野も網羅している．各雑誌に関して，X 線分析手法や測定された試料の傾向，分析技術や要素開発に関するトピックスの他に，特筆すべき論文には論評も記している．日本工業規格（JIS）におけるX線分析関連の規格の制定や改訂についてまとめている．X線関連メーカーのウェブサイトを紹介し，掲載している技術レポートの情報も得られる．　In this article, the interesting X-ray analysis-related literatures, which are published on academic journals during the year 2010, are summarized. The number of the researched journals is 19, including two Japanese journals, which contribute the advance of the X-ray analysis in the field not only of analytical chemistry but also of spectroscopy and physics. In every journal, the trend of the X-ray analysis methods and of the measured specimens, the topics of analytical technique and of the developed components of the X-ray analysis apparatus, and the comments for the nortable articles are mentioned. The constitution and revision of standards of X-ray analysis on Japanease Industrial Standard (JIS) are shown. The websites of the company related with X-ray tools or X-ray apparatus are also shown, and the information on technical reports is available