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In situ microscopic measurement is a novel approach to clarify the intrinsic mechanism of complexation reactions occurring at liquid/liquid interfaces. The present review was mainly focused on recent three topics of methodology of in situ fluorescence microscopic observation and measurement of interfacial complexation reactions: (1) two kinds of self-assemblies of Pd2+ and 5,10,15,20-tetra(4-pyridy1)-21H, 23H-porphine complexes formed at the toluene/water interface, (2) microextraction of Eu3+doi:10.5188/ijsmer.13.1 fatcat:t4c7v5yjhnew7grscmafgwjfua