Proton-switchable vapochromic behaviour of a platinum(II)-carboxy-terpyridine complex

We synthesized a carboxy-substituted Pt(II)-terpyridine complex, i.e. [PtCl(Hctpy)] Cl ([1H] Cl; Hctpy = 4'-carboxy-2,2': 6',2''-terpyridine), that shows interesting switchable vapochromic behaviour upon protonation/deprotonation of the carboxy group. The as-synthesized dark-blue amorphous-like solid [1H] Cl center dot 3H(2)O was converted to a yellow crystalline solid, [1H] Cl center dot H2O, upon exposure to various polar organic solvent vapours (e.g., acetonitrile, ethanol, 1-propanol, and dichloromethane), which promote the removal of water molecules. The reaction of [1H] Cl center dot 3H(2)O with aqueous ammonia afforded a deprotonated bright-yellow crystalline complex, i.e. [PtCl(ctpy)]center dot H2O (1 center dot H2O), which exhibits red luminescence with an emission maximum at 622nm. Although the colour of 1 center dot H2O was not affected by exposure to various polar organic solvent vapours, interesting vapochromic luminescence with a remarkable red-shift of the emission maximum from 622 to 652 nm was observed upon exposure to saturated water vapour to form orange crystalline 1 center dot 3.5H(2)O X-ray structural analysis revealed that the planar and neutral complex molecule 1 forms a one-dimensional columnar structure with an intermolecular Pt center dot center dot center dot Pt distance of 3.518(2) angstrom in the orange crystall 1 center dot 3.5H(2)O, while the cationic molecule [1H](+) in the protonated form, [1H] Cl center dot H2O, generates a dimeric structure with an intermolecular Pt center dot center dot center dot Pt distance of 3.439(2) angstrom. This difference suggests that the vapochromic behaviours of the protonated and deprotonated forms could be caused by structural changes induced by water-vapour adsorption/desorption, which affect the intermolecular Pt. Pt distance, thereby changing the energy of the metal-metal-to-ligand charge-transfer (MMLCT) transition. These contrasting results for the protonated and deprotonated complexes clearly indicate that the hydrophilicity of complex 1 is significantly affected by protonation/deprotonation of the carboxy group. In addition, quasi-reversible conversion between [1H] Cl center dot 3H(2)O and 1 center dot H2O was achieved by exposure of the protonated and deprotonated forms to triethylamine and humid hydrochloric acid vapours, respectively

Effect of Kampo Medicine on Pain and Range of Motion of Osteoarthritis of the Hip Accompanied by Acetabular Dysplasia: Case Report and Literature Review

We report a 52-year-old female with end-stage osteoarthritis of the hip accompanied by acetabular dysplasia in whom quality of life (QOL) was improved by Kampo treatment

情報リテラシー教育におけるプレゼンテーションのピアレビュー分析 : 医療福祉系短期大学における事例

　「情報科学実習」科目で実施した「総合演習課題」において学生が回答したピアレビューの内容を分析し，学生のプレゼンテーションにおける相互評価の基準の明確化を試みた。ピアレビューで回答のあったコメントを元にKJ法(蓄積された情報から関連するものを整理し統合する手法)による分類を行った結果，17の小カテゴリーが判明し，それらは大きく「発表内容に関する」「発表態度に関する」「スライドの出来に関する」「質疑応答・その他」の，４つのカテゴリーにまとめられた。最も多くのコメントが「発表内容に関する」カテゴリーであったが，グループごとの成績とカテゴリーを比較した場合，「スライドの出来に関する」カテゴリーが上位グループに集中していた。学生間の相互評価で高評価を得るためには，発表内容の精査はもちろん，ある程度のスライドのデザイン性が必要になることが分かった。To enhance students’ communication ability and learning effects, we introduced collaborativelearning into the class of ‘Practice of Information Literacy,’ and let students do group presentations and peer reviews. We analyzed the peer review comments posted by students, and tried to clarify evaluation standard of the student presentation. The comments responded were classified into 17 small groups by KJ method, and furthermore, they were categorized into four major groups; comments about “content of the presentation,” “announcement attitude,” “quality of the slides”, and “questions and answers and others”. More than half of the comments belonged to the category of “content of the presentation,” while much more comments on “quality of slides” seen in the highly rated groups. We confirmed that in mutual evaluation, students focus attention on not only the content of the presentation but slide design

Review Article : Feudalism or Absolute Monarchism?

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/68809/2/10.1177_009770049001600304.pd

Two-way vapochromism of a luminescent platinum(II) complex with phosphonic-acidfunctionalized bipyridine ligand

A luminescent Pt(II) complex [Pt(CN)(2)(H(4)dpbpy)] (1P; H(4)dpbpy = 2,2'-bipyridine-4,4'-diphosphonic acid) bearing a phosphonic-acid-functionalized bipyridine ligand was successfully synthesized and its unique two-way vapochromic behaviour investigated. X-ray structure analyses of both the anhydrous 1P and penta-hydrated 1P.5H(2)O phases clearly reveal the activation of intermolecular Pt. Pt interactions through the adsorption of water vapour. Emission spectroscopy reveals that the penta-hydrated 1P.5H(2)O complex exhibits an orange emission at 585 nm that shifts in two directions, to a blue-green emission at 469 nm by drying at 100 degrees C or to a red emission at 701 nm by drying under vacuum at room temperature. Thermogravimetric analyses and powder X-ray diffraction studies clearly reveal that anhydrous 1P, with negligible intermolecular Pt. Pt interactions, is formed by drying at 100 degrees C whereas the monohydrate 1P.H2O phase, with effective Pt. Pt interactions, is formed by drying under vacuum

Liquid-liquid interface-promoted formation of a porous molecular crystal based on a luminescent platinum(ii) complex

Porous molecular crystals (PMCs) should function as new-generation functional porous materials, but the selective crystallisation of PMCs is still difficult. Herein we demonstrate that the liquid-liquid interface between the MeOH/H2O mixture and alkanes promotes the crystallisation of a Pt(ii)-based PMC, rather than the nonporous form. This new crystallisation method allows control of not only the porosity but also the luminescence of the Pt(ii) complex crystal