Compositional analysis of metal chelating materials using near-field photothermal Fourier transform infrared microspectroscopy

Photothermal-Fourier transform-infrared (PT-FT-IR) microspectroscopy employs a thermal probe mounted in a scanning probe microscope (SPM). By placement of the tip of the probe on the surface of a solid sample, it can obtain localized IR spectra of a wide range of samples. A second mode of analysis is also available; a sample can be taken from the selected location using a technique called thermally assisted nanosampling (TAN), then a spectrum can be obtained of the nanosample while the probe is remote from the surface. We report a novel method of local compositional analysis that combines both of these types of measurement; a reagent is attached to the tip using TAN, then the reagent is placed in contact with analyte. IR spectroscopy can then be used to analyze any interaction between the reagent and surface it is placed in contact with. All of these modes of analysis were illustrated using a metal chelating agent. In the surface mode, changes to a solid bead of a chelating resin were measured using standard PT-FT-IR. In the nanosampling mode of analysis, a particle of a chelating polymer was attached to the tip of the probe using TAN and this was placed in contact with a concentrated calcium solution. Strong spectral changes were observed that mirrored those found when exposing the surface bound chelating resin bead to a solution of the same ion. A semiquantitative simulation of the PT spectrum for a chelating resin bead was achieved using a thermal diffusion model derived from photoacoustic spectroscopy indicating that semiquantitative or quantitative measurements will be possible in such a system.