Kinetic and equilibrium studies of ion association reaction between dye ions and hydrophobic counter ions accompanied by the change in light-absorbing and fluorescent characteristics

染料离子与疏水抗衡离子之间的离子缔合反应伴随光吸收和荧光特性变化的动力学和平衡研究

• 批准号: 03453043
• 负责人: MOTOMIZU Shoji
• 金额: $ 2.75万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453043/
• 关键词: Ion association; Phenylazophenol derivatives; Triphenylmethane dyes; Benzaurin derivatives; Malachite Green derivatives; Changes in light-absorption characteristics; Ionic surfactants; Heteropoly acid; アゾ系染料イオン; トリフェニルメタン系染料イオン; 界面活性剤; 水溶液反応

1. Four principles of characteristic light-absorption and fluorescence changes accompanied by ion association between dye ions and hydrophobic counter ions in an aqueous medium were found. To clarify the changes in characteristic light-absorption and establish useful color reactions based on ion associates, novel ionic dyes were synthesized and examined.2. N,N-dialkylaminophenylazobenzenesulfonic acid and its derivatives were synthesized. Dibutyl derivatives were found to show the most effective blue shift, when they formed ion associates with hydrophobic cations. This phenomena was useful in the absorptiometric determination of cationic and anionic surfactants in aqueous mediums. Derivatives of phenylazophenol were examined. These dyes showed a red shift and molar absorptivities became larger, when the polarity of a medium changed from polar to less polar. Novel anionic triphenylmethane dyes were synthesized. They were very stable even in an alkaline medium. In a weakly acidic medium, … More the electrically neutral species reacted with a hydrophobic cations to form colored ion associates. This color relation was favorably applied to the photometric titration of ionic surfactants as an indicator.3. Characteristics and behavior of triphenylmethane dyes in an aqueous medium were examined by a stopped-flow method. All rate and equilibrium constants were determined for five representative dyes. Halogeno derivatives of Malachite Green and Brilliant Green were newly synthesized and examined. These dyes were less hydrated and more hydrophobic. The monochloro derivative of MG was preferably used for the ion association with heteropolyacid. Dialkylaminophenylazopyridine derivatives were synthesized and examined. These dyes reacted with hydrophobic anions (A^-) to form ion associates (HD^+ ・ A^-). Dialkylaminophenylazo-N-alkyl- pyridinium salts was also synthesized and examined. In an acidic medium, the dyes were present in a protonated form(HD^<2+>), which reacted with hydrophobic anions(A^-) to form ion associates (D^+ ・ A^-), followed by the color change from yellow to reddish violet. Less

1.发现了水溶液中染料离子与疏水反离子缔合时特征光吸收和荧光变化的四个规律，为了阐明特征光吸收的变化规律，建立基于离子缔合的显色反应，合成并研究了新型离子染料.合成了N，N-二烷基氨基苯偶氮苯磺酸及其衍生物。二丁基衍生物被发现显示出最有效的蓝移，当它们形成离子缔合与疏水阳离子。这一现象可用于水介质中阳离子和阴离子表面活性剂的吸光光度测定。对苯偶氮苯酚的衍生物进行了研究。当介质的极性由强极性变为弱极性时，这些染料的摩尔吸光系数均发生红移。合成了新型阴离子型三苯甲烷染料。它们甚至在碱性介质中也非常稳定。在弱酸性介质中， ...更多信息 电中性物质与疏水阳离子反应形成有色离子缔合物。该颜色关系可作为指示剂用于离子型表面活性剂的光度滴定.用停流法研究了三苯甲烷类染料在水介质中的性质和行为。所有的速率和平衡常数，确定为五个代表性染料。本文报道了孔雀石绿绿色和亮绿色的卤代衍生物的合成和性质。这些染料的水化程度较低，疏水性较强。MG的一氯衍生物优选用于与杂多酸的离子缔合。合成了二烷基氨基苯基偶氮吡啶衍生物并对其进行了表征。这些染料与疏水阴离子（A^-）反应形成离子缔合物（HD^+ · A^-）。还合成并检测了二烷基氨基苯偶氮-N-烷基-吡啶盐。在酸性介质中，染料以质子化形式（HD^<2+>）存在，与疏水阴离子（A^-）反应形成离子缔合物（D^+ · A^-），随后颜色由黄色变为红紫色。少

项目成果

萩原 拓幸: "アゾ染料陽イオン・陰イオンおよびそれらのイオン会合体の水相/有機溶媒相界面への吸着平衡" 日本会学会誌. 720-728 (1992)

Takuy​​uki Hagiwara：“偶氮染料阳离子和阴离子的吸附平衡及其在水相/有机溶剂相界面的离子缔合”日本社会学学会杂志 720-728 (1992)。

S.Motomizu: "Novel indicator System for the photometric titration of ionic surfactants in an agues medium.Determination of anionic surfactants with distearyl dimethylammorium" Analyst(London). 117. 1775-1780 (1992)

S.Motomizu：“用于水凝胶介质中离子表面活性剂光度滴定的新型指示剂系统。用二硬脂基二甲基铵测定阴离子表面活性剂”分析师（伦敦）。

M.Oshima, S.Motomizu and H.Doi: "Interaction of hydrophobic anions with cationic dyes and its application to the spectrophotometric determination of anionic surfactants." Analyst (London). 117. 1643-1646 (1992)

M.Oshima、S.Motomizu 和 H.Doi：“疏水性阴离子与阳离子染料的相互作用及其在分光光度测定阴离子表面活性剂中的应用。”

K.Yamamoto: "Liguid-liguid distribution of ion associates of tetra halogenopalladate(II)with guaternary ammorium counterions." Solvent Extraction and Ion Exchange. 10. 459-476 (1992)

K.Yamamoto：“四卤代钯酸 (II) 与季胺抗衡离子的离子缔合体的液-液分布。”

T.Hagiwara, M.Oshima and S.Motomizu: "Adsorption equilibria of cationic and anionic azo dyes and their ion associates at water/organic solvent interface." Nippon Kagaku Kaishi. 720-728 (1992)

T.Hagiwara、M.Oshima 和 S.Motomizu：“阳离子和阴离子偶氮染料及其离子缔合物在水/有机溶剂界面的吸附平衡”。