title: Asynchronous orthogonal sample design scheme for two-dimensional correlation spectroscopy (2D-COS) and its application in probing intermolecular interactions from overlapping infrared (IR) bands.
abstract: This paper introduces a new approach to analysis of spectra called asynchronous orthogonal sample design (AOSD). Specifically designed concentration series are selected according to mathematical analysis of orthogonal vectors. Based on the AOSD approach, the interfering portion of the spectra arising strictly from the concentration effect can be completely removed from the asynchronous spectra. Thus, two-dimensional (2D) asynchronous spectra can be used as an effective tool to characterize intermolecular interactions that lead to apparent deviations from the Beer-Lambert law, even if the characteristic peaks of two compounds are substantially overlapped. A model solution with two solutes is used to investigate the behavior of the 2D asynchronous spectra under different extents of overlap of the characteristic peaks. Simulation results demonstrate that the resulting spectral patterns can reflect subtle spectral variations in bandwidths, peak positions, and absorptivities brought about by intermolecular interaction, which are barely visualized in the conventional one-dimensional (1D) spectra. Intermolecular interactions between butanone and dimethyl formamide (DMF) in CCl(4) solutions were investigated using the proposed AOSD approach to prove the applicability of the AOSD method in real chemical systems.
authors.affiliation: College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, PR China.
authors.forename: Xiaopei
authors.initials: X
authors.lastname: Li
authors.forename: Qinghua
authors.initials: Q
authors.lastname: Pan
authors.forename: Jing
authors.initials: J
authors.lastname: Chen
authors.forename: Shaoxuan
authors.initials: S
authors.lastname: Liu
authors.forename: Anqi
authors.initials: A
authors.lastname: He
authors.forename: Cuige
authors.initials: C
authors.lastname: Liu
authors.forename: Yongju
authors.initials: Y
authors.lastname: Wei
authors.forename: Kun
authors.initials: K
authors.lastname: Huang
authors.forename: Limin
authors.initials: L
authors.lastname: Yang
authors.forename: Juan
authors.initials: J
authors.lastname: Feng
authors.forename: Ying
authors.initials: Y
authors.lastname: Zhao
authors.forename: Yizhuang
authors.initials: Y
authors.lastname: Xu
authors.forename: Yukihiro
authors.initials: Y
authors.lastname: Ozaki
authors.forename: Isao
authors.initials: I
authors.lastname: Noda
authors.forename: Jinguang
authors.initials: J
authors.lastname: Wu
mesh_terms: D000465:Algorithms; D002074:Butanones / Q000737:chemistry; D002251:Carbon Tetrachloride / Q000737:chemistry; D004126:Dimethylformamide / Q000737:chemistry; D008956:Models, Chemical; D015203:Reproducibility of Results; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods*
chemical_list: D002074:Butanones; D004126:Dimethylformamide; D002251:Carbon Tetrachloride