System for fluorometry of carboxylic acids under mild condition

温和条件下羧酸荧光测定系统

• 批准号: 01860014
• 负责人: OHRUI Hiroshi
• 金额: $ 3.65万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B).
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01860014/
• 关键词: hydroxy fatty acid; hydroperoxy fatty acid; 9-bromomethylacridine; column switching; 9-ブロモメチルアクリジン; 蛍光分析; 脂肪酸; 高速液体クロマトグラフィ-; 9ーブロムメチルアクリジン; 脂肪酸の定量; プロスタグランジン; オカダ酸; HPLCの新分離条件; 9-acridinylmethyl ester; fatty acid; structural analysis; mas

9-Acridinylmethyl esters of fatty acids gave molecular ions with relatively strong intensity and simple fragmentation patterns. In the spectra of unsaturated fatty acid esters, the 26 mass unit separations were observed at the position of double bonds in the molecule. Ions (M-30)^+ and (M-31)^+ suggested the existence of a hydroxymethyl group and the 29 and 30 mass unit separations suggested the positions of hydroxy groups located in the molecule. These fragmentations were useful for the structural analysis of fatty acids.Hydroxy and hydroperoxy fatty acids were labeled with 9-bromomethylacridine at room temperature. They were separated from the degradation produce and less polar fatty acid derivatives on an octyl silicagel column, and were loaded into an octadecyl silicagel column by the on-line column switching. By the method, picomolar levels of the derivatives were determined with good reproducibility. The detection limit of 16-hydroxyhexadecanoic acid as a representative was 0.9 pmol (S/N=3) and the relative standard deviation of its peak areas was 2.5% (18.5 pmpl,n=7). The method was applied to the determination of the hydroxy fatty acids derived from phosphatidylcholine (PC) hydroperoxides spiked in human plasma. During the incubation at 37ﾟC for 4h, 2.5-3% of PC hydroperoxides decreased gave the corresponding hydroxy fatty acids.

9-吖啶基脂肪酸甲酯使分子离子具有较强的强度和简单的碎裂模式。在不饱和脂肪酸酯的光谱中，在分子中的双键位置观察到26个质量单位的分离。离子(M-30)^+和(M-31)^+表明了羟甲基的存在，29和30个质量单位的分离表明了羟基在分子中的位置。这些碎片对脂肪酸的结构分析是有用的。在室温下用9-溴甲基吖啶标记羟基和羟基过氧基脂肪酸。在辛基硅胶柱上将它们从降解产物和低极性脂肪酸衍生物中分离出来，并通过在线柱切换将它们装载到十八烷基硅胶柱中。用该方法测定了衍生物的皮摩尔水平，重现性好。以16-羟基十六酸为代表的检出限为0.9pmol(S/N=3)，峰面积的相对标准偏差为2.5%(18.5pmpl，n=7)。将该方法用于人体血浆中添加的磷脂酰胆碱(PC)过氧化氢衍生羟基脂肪酸的测定。在37ﾟC下孵育4h，2.5%~3%的过氧化氢还原生成相应的羟基脂肪酸。

项目成果

Kazuaki Akasaka: "Determination of Hydroxy and Hydroperoxy Fatty Acids by a High Performance Liquid Chromatography with a column Switching System"" Biosci. Biotech. Biochem.

Kazuaki Akasaka：“采用柱切换系统的高效液相色谱法测定羟基和氢过氧脂肪酸””Biosci. Biotech. Biochem.

Kazuaki Akasaka: "Determination of Hydroxy and Hydroperoxy Fatty Acids by a High Performance Liquid Chromatography with a column Switching System" Biosci.Biotech.Biochem.submited for publication.

Kazuaki Akasaka：“采用柱切换系统的高效液相色谱法测定羟基和氢过氧脂肪酸”Biosci.Biotech.Biochem.已提交出版。

Kazuaki AKASAKA: "Structural Analysis of aーAcridinylmethyl Derivatives of Fatty Acids by Mass Spectrometry" ANALYTICAL SCIENCES.6. 511-514 (1990)

Kazuaki AKASAKA：“通过质谱法对脂肪酸的α-吖啶基甲基衍生物进行结构分析”分析科学.6 (1990)。

Kazuaki Akasaka: ""Structural Analysis of 9-Acridinylmethyl Derivatives of Fatty Acids by Mass Spectrometry"" Analytical Sciences. Vol. 6. 511-514 (1990)

Kazuaki Akasaka：“通过质谱法对脂肪酸的 9-吖啶基甲基衍生物进行结构分析”，分析科学。

Kazuaki Akasaka: "Structural Analysis of 9-Acridinylmethyl Derivatives by Mass Spectrometry" Analytical Sciences.

Kazuaki Akasaka：“通过质谱法对 9-吖啶基甲基衍生物进行结构分析”分析科学。