The New Nomenclature of an Inorganic Compound

指導法・実践報

Radiotherapy for inoperable and refractory endometriosis presenting with massive hemorrhage: a case report

INTRODUCTION: Many patients with endometriosis are treated with medication or by surgical approaches. However, a small number of patients do not respond to medication and are inoperable because of comorbidities. This case report shows the effectiveness of radiotherapy for refractory endometriosis and includes a time series of serum estradiol levels. CASE PRESENTATION: A 47-year-old Asian woman presented to our facility with uncontrolled endometriosis refractory to medication. Our patient was considered inoperable because of severe idiopathic thrombocytopenic purpura, and underwent radiotherapy for massive genital bleeding requiring blood transfusions. A radiation dose of 20Gy in 10 fractions was delivered to the pelvis, including the bilateral ovaries, uterus, and myomas. An additional 10Gy in five fractions was delivered to the endometrium to control residual bleeding. Genital bleeding was completely inhibited on day 46 after radiotherapy. Hormonal analysis revealed that radiotherapy induced post-menopausal status. Two years after radiotherapy, atypical genital bleeding had not recurred and has been well controlled without side effects. CONCLUSIONS: Disrupted ovarian function is an adverse effect of radiotherapy. However, radiotherapy can be useful for inducing menopause. In cases of medication-refractory or inoperable endometriosis, radiotherapy would be an effective treatment option

<所内学術研究成果報告>H. <抗菌抗力ビ活性を有する水溶性銀 (I) 錯体の合成>

本研究では銀(I)-酸素結合をもつ水溶性銀(I)錯体として,グリシン,アスパラギン酸,アスパラギン,ヒスチジン,アラニンなどS原子を含まないアミノ酸によるいくつかの銀(I)錯体を合成した。単結晶X線構造解析,固体^Cおよび^N NMR,水溶液中の^1H, ^C NMRなどにより固体状態の構造と溶液中の構造の違いを明らかにした。銀原子の配位様式からアミノ酸銀錯体は4つのタイプ(Ag-O結合だけからなる錯体,O-Ag-OとN-Ag-N結合の両方を含む錯体,O-Ag-N結合からなる錯体,Ag-N結合だけからなる錯体)に分類できるが,本研究ではそれらを全て構造解析することができた。これらのアミノ酸銀(I)錯体はいずれも広いスペクトルの優れた抗菌抗力ビ活性を示した。構造と抗菌活性の相関について考察した。いくつかの銀(I)錯体について配位子交換性を調べた。関連する銀(I)錯体として,必ずしも水溶性ではないが,チオール基配位子による種々の銀錯体,複素環窒素配位子による種々の銀錯体,ヒノキチオール銀錯体,銀-酸素結合を有する種々の銀錯体などを合成し,それらの構造,抗菌活性を調べた。銀(I)錯体の抗菌活性のスペクトルは銀(I)錯体の配位子交換性と密接に関係していることを明らかにした

Synthesis, X-Ray Crystal Structures and Antimicrobial Activities of Transition-Metal Complexes with Hinokitiol Ligand

There exist at least three different polymorphs in the copper(II) complex [Cu(hino)_2] with a hinokitiol ligand (Hhino; 4-isopropyltropolone). In addition to deep-green plate crystals la and deep-green rod crystals Ib, whose crystal structures have been recently reported, novel green needle crystals Ic of [Cu(hino)_2] were found, the crystal structure of which was here determined by single-crystal X-ray analysis. Since only one crystal structure has been reported for the copper(II) complex [Cu(trop)_2] with a tropolone ligand (Htrop), the polymorphism found in the crystals of [Cu(hino)_2] would be due to the presence of the isopropyl group on the tropolone ring. The synthetic conditions giving the three polymorphs in good yields were found and the crystals were characterized with elemental analysis, FT-IR, TG/DTA and X-ray powder diffraction (XPD) measurements, as well as solution molecular weight measurements for la. The solid-state magnetic behaviors or the temperature-dependent magnetic susceptibilities were measured with Supercon-ductivity Quantum Interference Devices (SQUID): la showed a weak ferromagnetic interaction, Ib showed a paramagnetic nature with S = 1/2, while Ic showed a weak antiferro-magnetic interaction. The antimicrobial activities for selected bacteria, yeasts and molds were also measured in the water-suspension system\u27 la and Ib showed no activity, while 1c showed modest activities, and these activities were compared with those of the neutral Hino and the anionic hino ligands

L. チオセミカルバゾン三座配位子による金属錯体の合成と抗菌活性

The reaction of Ni(OAc)_2 with N\u27-[1-(2-pyridyl) ethylidene] morpholine-4-carbothiohydrazide (HL) afforded two nickel (II) complexes, [Ni(L)_2] (1) and [Ni(L)(OAc)] (2), depending on reaction temperature and starting molar ratio; the former was a 6-coordinate, paramagnetic complex and the latter a 4-coordinate, diamagnetic complex. X-ray analysis of the complex 2 revealed that the ligands, L and OAc, were coordinated to the central metal ion to form a square-planar geometry. The complex 2 showed enhanced antimicrobial activities against selected Gram-positive bacteria, compared with those of the ligand alone, whereas the other complex 1 showed no activity

ヒノキチオール金属錯体の合成、X線構造解析および抗菌活性

天然系抗菌剤のヒノキチオール(Hhino;4-イソプロピルトロボロン)を配位子とした銀(I)錯体を合成した。Hhinoのナトリウム塩[Na(hino)]・2H_2Oと硝酸銀(I)を水中でモル比1:1で反応させ、黄色の銀(I)錯体を得た(収率56.0%)。この錯体はDMSO,CHCl_3に可溶、水、アセトン、酢酸エチル、エーテルに不溶であった。溶液中で光に対して不安定であり、単結晶X線回折測定に適した結晶は得られなかった。既に構造解析されているD,L-アスパラギン酸による銀(I)の二核錯体[Ag_2(D-Hasp)(L-Hasp)]の結合距離、結合角のデータをreferenceにして、粉末X線回折データを用いたRietveld解析で構造解析を行った。この錯体はAg_2O_4をコアとしたAg-Ag結合(2.84A)もつ二核錯体[Ag(hino)]_2であった。この錯体はバクテリア、酵母、カビに対して広いスペクトルの抗菌活性を示した。抗菌性を示さないヒノキチオールコバルト(II)錯体[Co(hino)_2(EtOH)]_2やアルミニウム(III)錯体[Al(hino)_3]・MeOHの分子構造と比較して、銀-酸素結合錯体の抗菌作用を考察した。配位子hinoは銀イオンを生体系へ運搬する役割を果たしていると思われる

I. <種々の複素環窒素配位子による銀 (I) および金 (I) 錯体の合成と生理活性>

(1) Two novel polymeric silver (I)-triphenylphosphine complexes with nitrogen-containing heterocycles, [Ag (1,2,3-triz) (PPh_3)_2]_n 3 and [Ag (1,2,4-triz) (PPh_3)_2]_n 4 (Htriz=triazole) were synthesized from reactions of polymeric precursors [Ag (1,2,3-triz)]_n 1 and [Ag (1,2,4-triz)]_n 2 with 3 equiv of PPh_3 in CH_2Cl_2,respectively. The polymeric precursors 1 and 2 have been obtained as a non-crystalline, colorless powder-solid : 2 showed a wide spectrum of excellent antibacterial activities, but 1 did not. The antimicrobial activities of the complexes 1-4,evaluated by MIC (minimum inhibitory concentration), were compared and key factors affecting them were discussed. The crystal structures of the complexes 3 and 4 were determined by single-crystal X-ray diffraction. The complexes 3 and 4 in the solid-state were helical polymers consisting of AgN_2P_2 cores formed by bridging triazolate anions and two PPh_3 ligands. The complexes 3 and 4 were also fully characterized by elemental analyses, TG/DTA and FT-IR in the solid-state and by various solution NMR (^P, ^Ag, ^1H and ^C) spectroscopies and molecular weight measurements in solution. (2) Two novel gold (I)-triphenylphosphine complexes with nitrogen-containing heterocycles, [Au (1,2,3-L) (PPh_3)] 1 and [Au (1,2,4-L) (PPh_3)]_2・xH_2O (x=0.5-1.0) 2 (HL=triazole) were synthesized from stoichiometric reactions of a precursor complex [AuCl (PPh_3)] with HL in acetone in the presence of aqueous NaOH, and isolated as colorless needles and cubic crystals, respectively. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction. 1 and 2 were also fully characterized by complete elemental analyses, TG/DTA and FT-IR in the solid-state and by solution NMR (^P, ^1H and ^C) spectroscopies and solution molecular-weight measurements. 1 consisted of a monomeric 2-coordinate AuNP core both in the solid-state and in solution, while, in contrast, 2 comprised a dimeric (AuNP)_2 core through an Au-Au bond in the solid-state, but a monomeric AuNP core in solution. Within the two gold (I) complexes composed of very closely related nitrogen-containing heterocycles and a common bulky PPh_3,ligand, it was found that the aggregation through the Au…Au interaction in 2 was overruled in 1. The molecular structures of 1 and 2 were also compared with those of the corresponding silver (I) analogs, [Ag (1,2,3-L) (PPh_3)_2]_n 3 and [Ag (1,2,4-L) (PPh_3)_2]_n 4,the molecular structures of both of which have been recently determined as helical polymers in the solid-state. (3) Polymeric silver (I) imidazolate [Ag (imd)]_n (1; Himd=imidazole, C_3H_4N_2) showing a wide spectrum of excellent antimicrobial activities against bacteria, yeast and mold, which has been obtained as non-crystalline, colorless powder, was successfully converted to molecular, crystalline complex [Ag (imd) (PPh_3)_3] 2 by a reaction of 1 with 3 equivalents of PPh_3 in CH_2Cl_2. This novel complex 2 was not obtained from reactions in solutions of the precursors [AgCl (PPh_3)_3] and/or [AgCl(PPh_3)_2]_2 with Himd in the presence of NaOH or with sodium salt of imd. On the contrary, the corresponding gold (I) complex [Au (imd) (PPh_3)] 3 was formed by a reaction of the precursor [AuCl (PPh_3)] and Himd in the presence of NaOH. From a synthetic viewpoint, these facts show the ordering of ligand replacement in these complexes to be Ag-P>>Ag-Cl>Ag-N, while Au-P>>Au-N>Au-Cl. This ordering also exhibits the different reactivity of silver (I) and gold (I) complexes with biological ligands such as proteins, enzymes, nucleic acids and amino acids. The complex 2 was fully characterized by complete elemental analyses, TG/DTA, FT-IR, solution molecular weight measurement and various solution NMR (^1H, ^C, ^P and ^Ag) spectroscopies. The complex 2 in solution was present in a rapid equilibrium with the dissociated species of two PPh_3 ligands, i. e., [Ag (imd) (PPh_3)]. The ^P NMR measurements at low temperature showed that (i) all PPh_3 ligands in 2 in CHCl_3 solution migrated at room temperature between the two isotopes ^Ag and ^Ag, in addition to the dissociation of two PPh_3 ligands, and (ii) there were present the 4-coordinate tetrahedral complex 2 and the dissociated complex [Ag (imd) (PPh_3)] in solution

C-5. ベンゼンのヒドロキシル化反応に対する修飾ヘテロポリ酸塩を利用した触媒設計

Using selectively site-substituted vanadium (V) Keggin and Dawson heteropolytungstates (HPA), the catalytic activities for hydroxylation of benzene in the presence of 30% aqueous H_2O_2 were examined at room temperature under atmospheric pressure in a two liquid phase, aqueous and organic process. In particular, potassium salts of di- and tri-vanadium (V) substituted Keggin HPAs, α-1,2-PW_V_2 and α-1,2,3-PW_9V_3,showed 0.81 and 8.69 catalytic turnovers for phenol production with excellent selectivity, respectively, for 48h reaction under the conditions : 0.1mmol catalyst, 1mL(11.3mmol) benzene, 2mL of acetonitrile and 2mL of 30% H_2O_2. The activity of tri-substituted, PW_9V_3,HPA was initially high, but it maximized after 48h and its structure completely decomposed, whereas that of di-substituted, PW_V_2,HPA gradually increased and exceeded that of the PW_9V_3 after 120h. The polyoxoanion structure of the PW_V_2 was maintained even after 576h. Their activities and stabilities as catalysts were compared with those of vanadium (V)-substituted Dawson HPAs (α-P_2W_V and α-1,2,3-P_2W_V_3), vanadium (V)-containing isopolyanions (IPA; VW_5 and V_), the Milas reagent (V_2O_5 and aqueous H_2O_2), and the picolinato-vanadium (V) oxo peroxo complex