Sensitivity enhancement via multiple contacts in the {1H–29Si}–1H cross polarization experiment: a case study of modified silica nanoparticle surfaces

{¹H–²⁹Si}–¹H double cross polarization inverse detection (DCPi) solid-state NMR, has recently been shown to be a powerful tool for studying molecules adsorbed on the silica surface. In this contribution, we develop an improved version (MCPi) which incorporates a block of multiple contact pulses, and quantitatively compare the sensitivities of MCPi and DCPi over a typical range of experimental parameters. The MCPi pulse sequence aims at higher sensitivity and robustness for studying samples with various relaxation characteristics. In the case of dimethyl sulfoxide (DMSO) molecules adsorbed on the silica surface, MCPi performs equally well or up to 2.5 times better than DCPi over a wide range of parameters. The applicability to and performance of MCPi on composite materials was demonstrated using a sample of polymer–silica composite, where significantly higher sensitivity could be achieved at very long total mixing times. The results also showed that both techniques are surface specific in the sense that only the groups close to the surface can be detected.

In this paper we demonstrate {¹H–²⁹Si}–¹H multiple cross polarization inverse detection (MCPi) solid state NMR as a robust technique for studying modified silica nanoparticle surfaces.