In situ studies of metal coordinations and molecular orientations in monolayers of amino-acid-derived Schiff bases at the air-water interface.
The surface behaviors of monolayers of amino-acid-derived Schiff bases, namely, 4-(4-(hexadecyloxy)benzylideneamino)benzoic acid (HBA), at the air-water interface on pure water and ion-containing subphases (Cu2+, Ca2+, and Ba2+) have been clarified by a combination of surface pressure-area isotherms and surface plasmon resonance (SPR) technique, and the metal coordinations and molecular orientations in the monolayers have been investigated using in situ infrared reflection absorption spectroscopy (IRRAS). The presence of metal ions gives rise to condensation of the monolayers (Cu2+, pH 6.1; Ca2+, pH 11; Ba2+, pH 10), even leading to the formation of three-dimensional structures of the compressed monolayer in the case of Ba2+ (pH 12). The metal coordinations with the carboxyl groups at the interface depend on the type of metal ions and pH of the aqueous subphase. The orientations of the aromatic Schiff base segments with surface pressure are elaborately described. The spectral behaviors of the Schiff base segments with incidence angle in the case of Ba2+ (pH 12) have so far presented an excellent example for the selection rule of IRRAS at the air-water interface for p-polarization with vibrational transition moments perpendicular to the water surface. The chain orientations in the monolayers are quantitatively determined on the assumption that the thicknesses of the HBA monolayers at the air-water interface are composed of the sublayers of alkyl chains and Schiff base segments.
MOE Key Laboratory of Mesoscopic Chemistry, State Key Laboratory of Coordination Chemistry, and School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China.
Huijin
H
Liu
Haifu
H
Zheng
Wangen
W
Miao
Xuezhong
X
Du
D000388:Air; D001464:Barium / Q000737:chemistry; D019817:Benzoic Acid / Q000737:chemistry; D002118:Calcium / Q000737:chemistry; D002621:Chemistry / Q000379:methods*; D003300:Copper / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D007477:Ions; D008670:Metals / Q000737:chemistry*; D008956:Models, Chemical; D012545:Schiff Bases / Q000737:chemistry*; D020349:Surface Plasmon Resonance; D013499:Surface Properties; D013997:Time Factors; D014867:Water / Q000737:chemistry
D007477:Ions; D008670:Metals; D012545:Schiff Bases; D014867:Water; D001464:Barium; D003300:Copper; D019817:Benzoic Acid; D002118:Calcium