Research of Blueness : Lapis Lazuli in the Kizil Grottoes Murals of the Silk Road

The primary purpose of this thesis is to clarify the role and origin of the lapis lazuli used in the Kizil Grottos in China. Particularly, it will seek to clarify how lapis lazuli was used, where it came from and who used it. The paper begins by considering the techniques used for purifying lapis lazuli, as well as its different uses. Following this, I consider the both the layout of and the different shades of blue present in the Kizil Grottoes Murals, as well as how the different shades were used to emphasise the importance of motifs. The purification of lapis lazuli, used to produce different types of blue colour, has a long history, and it has changed along with the development of new chemicals. This paper tries to illuminate how the different variations of the concept of “blueness”, expressed by three different Japanese kanji (Chinese characters), 青(ao) 碧(ao) 蒼(ao), influenced the roles and use of these different types of blue in the murals found in the Kizil Grottoes. This paper also considers the origin of the lapis lazuli in the Kizil Grottoes. Lapis lazuli used in the Silk Road has until now been believed to have been exclusively produced in Afghanistan; however, this thesis presents findings that cast doubt on this commonly accepted theory since lapis lazuli was present in significant amounts only in the 224th cave in Kizil. Instead, I propose the hypothesis that the lapis lazuli used in the 224th cave was not from Afghanistan but a much nearer place, namely, the Tibet and Qinghai regions of China. The study of art techniques and painting materials provides the primary theoretical background for this paper; however, other studies are also consulted. Specifically, archaeological and historical studies of the Silk Road, studies of the Kizil Grottoes, as well as other studies from the fields of linguistics, Buddhist studies, and art history, are all also extensively consulted

Out-of hospital cardiac arrest in Okayama city (Japan): outcome report according to the "Utstein Style".

The purpose of this study was to evaluate the outcomes for out-of-hospital cardiac arrest (OHCA) and cardiopulmonary resuscitation (CPR) in the city of Okayama, Japan, during a 1-year period after the reorganization of defibrillation by Emergency Life-Saving Technicians (ELSTs) with standing orders of CPR. The data were collected prospectively according to an Utstein style between June 1, 2003 and May 31, 2004; OHCA was confirmed in 363 patients. Cardiac arrest of presumed cardiac etiology (179) was witnessed by a bystander in 62 (34.6%) cases. Of this group, ventricular fibrillation (VF) was documented in 20 cases (32.3%), and 1 patient (5%) was discharged alive without severe neurological disability. This outcome is average in Japan, but it is quite low level compared with Western countries because there is less VF in Japan. The Utstein style revealed that we must try to detect VF before the rhythm changes and to provide defibrillation as soon as possible in order to improve outcomes. Further research will be required to accurately evaluate OHCA in Okayama city.</p

Hetero and lacunary polyoxovanadate chemistry: Synthesis, reactivity and structural aspects

Many synthetic methods for heteropolyoxovanadates and lacunary polyoxovanadates have been developed in recent years. We outline various approaches used to produce new polyoxovanadate species, including heterometal-incorporated complexes of tetravanadates, hexavanadates, decavanadates and dodecavanadates. In particular, three types of synthetic routes are explored; based on (i) coordination of metavanadate species to transition metal cations, (ii) oxidation of reduced polyoxovanadates, and (iii) template synthesis. Metavanadate species can coordinate to metal cations as inorganic macrocyclic ligands to form heteropolyoxovanadates. The incorporation of a heterometal cation into decavanadates has also been reported. The oxidation reaction of reduced polyoxovanadates provides a new route to the formation of the lacunary polyoxovanadates, which can serve as inorganic host molecules. Dodecavanadates are bowl-type molecules of particular structural interest; a chloride anion can be incorporated into the bowl through a template synthesis. Structural transformations between these dodecavanadate species and alkoxopolyoxovanadates are also described. © 2011 Elsevier B.V

Synthesis and characterisation of some metal complexes of hybrid phosphorus-nitrogenligands: the crystal structure of 1-(diphenylphosphino)-2-(2-pyridyl)ethane cobalt(II) chloride

Some iron(II), cobalt(II) and copper(II) complexes of the hybrid ligand 1-(diphenylphosphino)-2-(2-pyridyl)ethane (dppe) and diphenyl-2-pyridylphosphine (dppp) have been synthesised and characterised. Analyses suggest tetrahedral structures in which the metal atoms are bonded to two chlorine atoms and to both phosphorus and nitrogen atoms for 1-(diphenylphosphino)-2-(2-pyridyl)ethane on one hand and on the other hand, bonding is through the nitrogen atoms of two molecules of diphenyl-2-pyridylphosphine, which acts as a monodentate ligand. The crystal structure of 1-(diphenylphosphino)-2-(2-pyridyl)ethane cobalt(II) chloride shows a pseudo-tetrahedral structure in which the aminophosphine is bonded to the cobalt centre through both the phosphorus and nitrogen atoms, forming a 6-membered ring.&#160;KEY WORDS: Aminophosphines, Metal complexes, Cobalt(II) complex, Crystal structure&#160;&#160;Bull. Chem. Soc. Ethiop. 2008, 22(2), 253-260

キュバン骨格を持つオキソ架橋鉄クラスターの合成と構造

金沢大学理学部本研究は、多彩な構造の化合物群を期待できる鉄-酸素原子骨格からなる多核錯体の一般的合成法を確立しようとする試みである。その過程でμ-アルコキソ鉄二核錯体の合成と酸素との反応性について次項にある雑誌論文に発表した。μ-アルコキソ鉄二核錯体と酸素との反応により平面型四核錯体を単離することもできた。そこで、金属酸素錯体を経由する多核化経路を検討することとした。しかし、たとえばキュバン骨格のように当初計画した三次元的に金属の配置したクラスターの単離には成功しなかった。これは、塩基性条件下での水酸化鉄の生成に妨げられたためである。そこで、より安定な酸素錯体を形成するコバルト三価種を用いる研究に進展した。具体的にはCO(acac)_3とme-tacn(1,4,7-trimethyl-1,4,7-triazacyclononane)の塩基性条件、酸素雰囲気下および過酸化水素との反応により三種類の錯体を単離した。単核アルコキソ錯体[Co(me-tacn)(acac)(OMe)]^+,酸素錯体[{Co(me-tacn)(acac)}_2(μ-O)_2]^,およびジスーパーオキソ架橋錯体[{Co(me-tacn)}_2(μ-OH)(μ-O)_2]^である。コバルトではより酸素錯体が安定であるため酸素錯体の生成は十分予想できることであるが、ヒドロキソおよびジスーパーオキソ架橋錯体というきわめて珍しい基本骨格を持つ混合原子価コバルト二核錯体を単離することができた。これらの錯体は通常の分析手段によって同定され、単結晶を用いて構造解析を行った。ジスーパーオキソ架橋錯体は単純な酸化還元挙動を示し、Co(III,III),Co(II,III),Co(II,II)のそれぞれの酸化状態を定電位電解により単離できる。現在ジスーパーオキソ架橋錯体の分解経路からのコバルト-酸素原子骨格からなるクラスターの合成を検討している。研究課題/領域番号:07854039, 研究期間(年度):1995出典：研究課題「キュバン骨格を持つオキソ架橋鉄クラスターの合成と構造」課題番号07854039（KAKEN：科学研究費助成事業データベース（国立情報学研究所）） （https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-07854039/）を加工して作

テンプレート反応を利用した半球状バナジウム酸化物分子の構築反応

超伝導,磁性,半導体,触媒能など現代文明を支えるハイテク化合物の多くに酸化物が用いられている。最高の性質を求めると酸化物にたどり着き,その分子レベルでの理解が重要となる。しかし,酸化物を分子として合成することは意外にも難しく,前人未踏の世界が広がっている。本研究において,酸化物イオンが金属イオンに配位した完全無機錯体の化学を発見し,錯体化学を無機物質にまで拡張できることを証明した。ルイス酸であるさまざまな金属イオンを,バナジウムオキソ酸からポリ酸といわれるオリゴマー酸化物分子を形成し,ヘテロ原子としての遷移金属を取り込んだ酸化物分子を合成した。(Bu_4N)[VO_3]溶液にさまざまな金属塩を加えると,そのルイス酸性によりバナジン酸の縮合反応が進行し,クラウンエーテルと似た環状酸化物[VO_3]_n^イオンが生成する。Co(II),Ni(II),Cu(II),Zn(II)イオンを無水条件で反応させることで,さまざまな環員数nの大環状無機錯体[M_1(VO_3)_n]^ を合成した。これは,環状ポリオキソバナデートが,クラウンエーテルのように金属に配位した無機配位子による配位化学である。また,環状無機錯体から,金属を取り除くとディスク状の酸化物骨格が残され,テンプレート存在下に縮合反応を行わせると,環状酸化物を入り口にしたお椀型のクラスターから球状のクラスターへと骨格変換される。硝酸イオンをテンプレートに用いると,驚くべきことにDNA二重らせんに類似した,バナジウムV8リボンの二重鎖からなる無機不斉分子への発見につながった。戦略的な基礎化合物である酸化物にヘテロ原子として種々の遷移元素を取り込んだ「分子」を,錯体合成できることを立証し,初めて無機二重らせん分子を発見した。本研究により,無機配位子を実際に有効に機能させ興味深い酸化物分子を多数開拓できたので,今後は機能性物質への展開が望まれる。Metal oxide is one of a popular material in high-tech world in modern society such as superconductivities, magnetic or semiconductor properties, and catalysts. When we look for the best properties of all, many of these materials are turning up to be metal oxides, and need to understand those properties from the molecular level. The synthesis of metal oxide as a molecule is seemingly easy, but is a challenge for a chemist for a long time, and unexplored world is wailing. In this study, we discover the chemistry of inorganic complex in which the oxide anion is coordinated to the metal atoms, and we proved the coordination chemistry can be expanded to the world of pure inorganic oxide chemistry. The inorganic complex was achieved by the combination of polyoxovanadates and the metal cations as Lewis acid The Lewis acidity of the metal sources prompt the condensation reaction of the metavanadate species, which is tri or tetramer in acetonitrile solution. The resulting pureinorganic complex of an, Ni(II), Cu(II), and Zn(II) have been synthesized in non-aqueous solution and various oxide molecule with crown-type oxide anion ligands were synthesized. Most of the interesting finding in this study is a discovery of the chiral inorganic molecule. When we condense the vanadate under the presence of nitrate template, we found the formation of two octadecavanadate chains through the nitrate template capped the both ends of the chain by V05 pyramidal units. In other view, the first double helical inorganic molecule had been emerged.The new chemistry of fundamental oxide of vanadium is strategic importance, and the understanding of the variety of properties in oxide can be tackled from the point of molecular chemistry. This study explorer the chemistry of oxide molecule and many interesting formation of disk, cage, chiral oxide molecule have been realized, and further studies will provide the extention toward the functional materials.研究課題/領域番号:16550051, 研究期間(年度):2004-2007出典：「テンプレート反応を利用した半球状バナジウム酸化物分子の構築反応」研究成果報告書　課題番号16550051 (KAKEN：科学研究費助成事業データベース（国立情報学研究所）)　　　本文データは著者版報告書より作

新しい骨格を持つオキソ架橋金属クラスターの合成

金沢大学理学部研究課題/領域番号:03740314, 研究期間(年度):1991出典：研究課題「新しい骨格を持つオキソ架橋金属クラスターの合成」課題番号03740314（KAKEN：科学研究費助成事業データベース（国立情報学研究所）） （https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-03740314/）を加工して作

Life and How to Live It

The reaction of Mn^III salen-type complexes with di- and tetraanionic α-Keggin-type polyoxometalates (POMs) was performed, and three types of Coulombic aggregations containing Mn^III out-of-plane dimeric units (abbreviated as [Mn₂]²⁺) that are potentially single-molecule magnets (SMMs) with an <i>S</i>_T = 4 ground state were synthesized: [Mn₂(5-MeOsaltmen)₂(acetone)₂]­[SW₁₂O₄₀] (<b>1</b>), [Mn₂(salen)₂(H₂O)₂]₂[SiW₁₂O₄₀] (<b>2</b>), and [Mn­(5-Brsaltmen)­(H₂O)­(acetone)]₂[{Mn₂(5-Brsaltmen)₂}­(SiW₁₂O₄₀)] (<b>3</b>), where 5-Rsaltmen^2– = <i>N</i>,<i>N</i>′-(1,1,2,2-tetramethylethylene)­bis­(5-R-salicylideneiminate) with R = MeO (methoxy), Br (bromo) and salen^2– = <i>N</i>,<i>N</i>′-ethylenebis­(salicylideneiminate). Compound <b>1</b> with a dianionic POM, [SW₁₂O₄₀]^2–, is composed of a 1:1 aggregating set of [Mn₂]²⁺/POM, and <b>2</b>, with a tetraanionic POM, [SiW₁₂O₄₀]^4–, is a 2:1 set. Compound <b>3</b> with [SiW₁₂O₄₀]^4– forms a unique 1D coordinating chain with a [−{Mn₂}–POM−]^2– repeating unit, for which a hydrogen-bonded dimeric unit ([Mn­(5-Brsaltmen)­(H₂O)­(acetone)]₂²⁺) is present as a countercation. Independent of the formula ratio of [Mn₂]²⁺/POM, Mn^III dimers and POM units in <b>1</b>–<b>3</b> form respective segregated columns along a direction of the unit cell, which make an alternate packing to separate evenly identical species in a crystal. The nearest intermolecular Mn···Mn distance is found in the order <b>2</b> < <b>3</b> < <b>1</b>. The segregation of the [Mn₂]²⁺ dimer resulted in interdimer distances long enough to effectively reduce the intermolecular magnetic interaction, in particular in <b>1</b> and <b>3</b>. Consequently, an intrinsic property, SMM behavior, of Mn^III dimers has been characterized in this system, even though the interdimer interactions are still crucial in the case of <b>2</b>, where a long-range magnetic order competitively affects slow relaxation of the magnetization at low ac frequencies

Synthesis and characterization of fluoride-incorporated polyoxovanadates

The speciation studies of oxovanadates are essential to clarify their biological activities. We surveyed the distribution of oxovanadate species in the presence of halide anions with various acid concentrations in an aqueous mixed-solvent system. The presence of chloride, bromide, and iodide anions has no effects on the appearance of polyoxovanadate species observed in 51V NMR. Those are the precedent formation of metavanadate species and decavanadates. The presence of fluoride anion during the addition of acids exhibits strong intervention in the polyoxovanadate equilibria and we found the subsequent formation of two polyoxovanadate species by 51V NMR observation. From the estimated experimental condition, we isolated fluoride-incorporated polyoxovanadates {Et4N}4[V7O19F] and {Et4N}4[HV11O29F2], successfully. Polyanion [V7O19F]4 - is the fluoride-incorporated all V(V) state polyoxovanadate which has two different coordination environments of tetrahedral and square pyramidal vanadium units within the one anionic structural integrity. The structural gap between tetrahedral-unit-based metavanadate and octahedral-unit-based decavanadate structures may be linked by this hybrid complex. © 2015 Elsevier Inc. All rights reserved.Embargo Period 24 month