Study of Solution Structure of Vanadium (III) Complexes by FT Raman Spectroscopy

傅里叶变换拉曼光谱研究钒(III)配合物的溶液结构

• 批准号: 07454174
• 负责人: KANAMORI Hiroshi
• 金额: $ 4.67万
• 依托单位: Toyama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454174/
• 关键词: vanadium; complex; solution structure; Raman spectrum

Raman spectra of several vanadium compounds, mainly in the +3 oxidation state, were measured with a view toward exploring the chemical structure and the physiological and biochemical functions of vanadium in the blood cells of ascidians (marine invertebrate), and some fundamental knowledge concerning a characterization and structure of vanadium compounds in solution. Firstly, Raman spectra of a homogenate of ascidian blood cells were obtained. The blood cells of ascidia samea were separated into two fractions, namely, giant cell rich (GC) and signet-ring cell rich (SRC) fractions, and the Raman spectrum of each fractions was measured. Both fractions exhibited the bands which are assignable to hydrosulfate anion or alkyl sulfonates and also the band due to free sulfate. The band due to vanadium ion could not be measured for both fractions. The concentration of vanadium in ascidia samea would be lower than the detection limit of the present FT Raman spectrometer. On the other hand, a blood cell homogenate of ascidia gemmata did show the band due to vanadyl group in addition to the band of free sulfate. In order to examine the interaction between vanadium (III) or- (IV) and sulfate ion, the Raman spectra of aqueous solution of V_2(SO_4)_3 and VOSO_4 were measured. The Raman spectra of both systems showed the bands whichi are assignable to sulfate anion coordinated to vanadium center, in addition to the band due to free sulfate, indicating that sulfate anion derectly bounds to vanadium ion in aqueous solution. Ascidians sequester vanadium (V) ions from seawater, reduce them to +3 oxidation state, and accumulate in their blood cells. Then, it is of importance to correlate the solution structure of vanadate species with their vibrational frequencies. We, therefore, examined the pH dependence of the Raman spectra of vanadate (V) and assigned the observed Raman bands to each oligomeric species.

测量了多种钒化合物（主要是+3氧化态）的拉曼光谱，旨在探讨钒在海鞘（海洋无脊椎动物）血细胞中的化学结构和生理生化功能，以及溶液中钒化合物的表征和结构的一些基础知识。首先，获得海鞘血细胞匀浆的拉曼光谱。将海鞘的血细胞分离成两个级分，即富含巨细胞(GC)和富含印戒细胞(SRC)的级分，并测量每个级分的拉曼光谱。两个级分都显示出归属于硫酸氢根阴离子或烷基磺酸根的谱带以及由于游离硫酸根而产生的谱带。对于这两个级分，无法测量由钒离子引起的谱带。海鞘中钒的浓度将低于现有FT拉曼光谱仪的检测限。另一方面，海鞘的血细胞匀浆除了游离硫酸盐的条带之外还显示出由氧钒基引起的条带。为了考察钒(III)或-(IV)与硫酸根离子之间的相互作用，测量了V_2(SO_4)_3和VOSO_4水溶液的拉曼光谱。两个系统的拉曼光谱显示，除了游离硫酸根引起的带外，还显示可归属于与钒中心配位的硫酸根阴离子的带，表明硫酸根阴离子直接与水溶液中的钒离子结合。海鞘从海水中螯合钒 (V) 离子，将其还原至 +3 氧化态，并积聚在其血细胞中。然后，将钒酸盐物质的溶液结构与其振动频率相关联非常重要。因此，我们检查了钒酸盐 (V) 拉曼光谱的 pH 依赖性，并将观察到的拉曼谱带分配给每个低聚物种类。

项目成果

金森寛 他2名: "Heptacoordinate Vanadium(III) Complexes Containing a Didentate Sulfate Ligand X-Ray Structures of {V_2(SO_4)_3{N,N'-bis(2-pyridylmethy)-1,2-ethanediamine}_2}and {V(SO_4){N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-cthanediamine}} and their solution

Hiroshi Kanamori 和另外 2 人：“含有二齿硫酸盐配体的七配位钒 (III) 配合物 {V_2(SO_4)_3{N,N-bis(2-pyridylmethy)-1,2-乙二胺}_2} 的 X 射线结构和{V(SO_4){N,N,N,N-四(2-吡啶基甲基)-1,2-乙二胺}}及其溶液

金森寛: "Aqua (ehtylenediamine-N,N'-diacetato) oxovanadium (IV)" Acta Crystallographica. (印刷中). (1997)

Hiroshi Kanamori：“Aqua（乙二胺-N,N-二乙酸）氧钒 (IV)”《晶体学报》（出版中）。

Kanamori, K., Kinebuchi, Y., and Michibata, H.: "Reduction of Vanadium (IV) to Vanadium (III) by Cysteine Methyl Ester in Water in the Presence of Amino Polycarboxylates" Chem.Lett.No.5. 423-424 (1997)

Kanamori, K.、Kinebuchi, Y. 和 Michibata, H.：“在氨基多羧酸盐存在下，水中的半胱氨酸甲酯将钒 (IV) 还原为钒 (III)”Chem.Lett.No.5。

金森寛 他2名: "Reduction of Vanadium(IV) to Vanadium (III) by Cysteine Methyl Ester in Water in the Presence of Amino Polycarboxylates" Chemistry Letters. 5. 423-424 (1997)

Hiroshi Kanamori 等 2 人：“在氨基多羧酸盐存在下，水中半胱氨酸甲酯将钒 (IV) 还原为钒 (III)”，《化学快报》5. 423-424 (1997)。

金森寛: "Heptacoordinate Vanadium (III) Complexes Containing a Didentate Sulfate Ligand." Bulletin of the Chemical Society of Japan. 69・10. 2901-2909 (1996)

Hiroshi Kanamori：“含有二齿硫酸盐配体的七配位钒 (III) 配合物”。日本化学会通报 69・10（1996 年）。