In-Situ Measurements and Molecular Orientation by External Reflection Spectrometry of Liquid-Liquid Interfacial Adsorbates of Porphyrins.

通过外反射光谱法对卟啉液-液界面吸附物进行原位测量和分子取向。

• 批准号: 13650865
• 负责人: MORIYA Yoshio
• 金额: $ 0.51万
• 依托单位: Akita University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650865/
• 关键词: liquid-liquid interface; protonated porphyrins; interfacial adsorbate; external reflection; partial internal reflection; molecular orientation; interface selection rule; aggregate; 吸着状態; 界面配向; p-偏光スペクトル; 界面濃度; 部分反射; J-会合体

The authors investigated the interfacial adsorption states of lipophilic-porphyrins (H_2P) in a protonated form (H_4PX_2) at the inert organic solvent/aqueous inorganic acid (HX) solution interface by development of in situ measurement devices for partial reflection spectrometry, including external reflection (ER) and partial internal reflection (PIR).1.Stoichiometric analysis of protonated tetraphenylporphyrin in an aggregate (H_4PX_2)_<n,i> was accomplished using a simple device comprising a liquid cell and prisms. (1)In the toluene-4 M H_2SO_4 system, ER spectrometry was effective to distinguish interfacial adsorbates from lipophilic solute in the organic phase (H_2P)_o. (2)In the dodecane-4 M H_2SO_4 system, all (H_2P)_o was protonated to yield (H_4PX_2)_<n,i> and aqueous species, H_4P^<2+>_<aq>. The relationship of reflection absorbance at each of bands for interfacial molecular density [H_4PX_2]_i suggested that the interfacial adsorption state changed from a monolayer form to a … More multilayer one with a different reflection coefficient. (3)The saturated interfacial molecular density in the dodecane-4 M H_2SO_4 system was estimated to be 1.20×10^<-10> mol cm^<-2> ; it yields a tilt angle 47°of pyrrole ring plane against the interface normal.2.No aggregation was found in the lipophilic tetraphenylporphyrin derivatives with substituent at ortho-position in meso-phenyl group. Whereas, protonated tetra-p-torylporphyrin could associate to form some aggregate. These suggest the molecular association is depend on the rotation nature of phenyl-group to yield a planar-type molecular structure.3.The incident angle dependence of reflection spectra was studied using a home-made variable-angle device. Positive and negative bands have been observed in the p-polarized PIR spectra, whose band location correspond to those in p-polarized ER spectra. Nevertheless, the bands in the p-PIR exhibited reversed sign to those of p-ER spectra. These suggest that the interface selection rule of the p-PIR spectrometry has a reversal rule of p-ER, and PIR can also be used for the analysis of molecular orientation. Less

通过研制部分反射光谱的现场测量装置，包括外反射(ER)和部分内反射(PIR)，研究了亲脂性卟啉(H_2P)质子化形式(H_4PX_2)在惰性有机溶剂/无机酸(HX)水溶液界面上的界面吸附状态。1.用一种由液室和棱镜组成的简单装置完成了质子化四苯基卟啉聚集体(H_4PX_2)的计量分析。(1)在甲苯-4-M H_2SO_4体系中，电流变光谱能有效地区分有机相(H_2P)_o中的界面吸附物和亲脂溶质。(2)在十二烷-4-H_2SO_4体系中，所有(H_2P)_o被质子化得到(H_4Px_2)_n，i&gt；和水物种H_4p^&lt；2+&gt；界面分子密度在各带的反射吸收关系[H_4Px_2]_i表明，界面吸附状态由单层状态转变为…状态更多的多层，具有不同的反射系数。(3)在十二烷-4-H_2SO_4体系中，饱和界面分子密度为1.20×10~(-10)~(-2)·m~(-2)，吡咯环平面相对于界面的倾斜角为47°。而质子化的四对甲苯基卟啉可以缔合形成一定的聚集体。这表明分子缔合作用依赖于苯基的旋光性质，从而形成平面型分子结构。3.利用自制的变角装置研究了反射光谱的入射角依赖关系。在p极化的PIR光谱中观察到了正带和负带，其位置与p极化的电流变光谱中的位置相对应。然而，p-PIR中的谱带与p-ER光谱中的谱带符号相反。这些结果表明，p-PIR光谱的界面选择规则具有与p-ER相反的规则，PIR也可用于分子取向分析。较少

项目成果

Nobuaki Ogawa, et al.: "Interfacial orientation of porphyrin at the liquid-liquid interface using UV-vis external reflection spectroscopy"Proceedings of the International Solvent Extraction Conference. ISEC2002. 58-63 (2002)

Nobuaki Okawa 等人：“使用紫外可见外反射光谱法在液-液界面处进行卟啉的界面取向”国际溶剂萃取会议论文集。

Yoshio Moriya, et al.: "Utilization of Partial Reflection Spectrometry for the Analysis of a Liquid-Liquid Interfacial Adsorbate"Scientific and Technical Reports of Faculty of Engineering and Resource Science, Akita University, Annual reports. No.24. 11-1

Yoshio Moriya 等人：“利用部分反射光谱法分析液-液界面吸附物”秋田大学工程与资源科学学院的科学技术报告，年度报告。

Yoshio Moriya: "Utilization of Partial Reflection Spectrometry for the Analysis of a Liquid-Liquid Interfacial Adsorbate"Scientific and Technical Reports of Faculty of Engineering and Resource Science, Akita University. Annual report No.24. 11-18 (2003)

Yoshio Moriya：“利用部分反射光谱法分析液-液界面吸附物”秋田大学工程与资源科学学院的科学技术报告。