Surface-assisted
laser desorption/ionization (SALDI) mass spectrometry (MS) has become
an attractive complementary approach to matrix-assisted laser desorption/ionization
(MALDI) MS. SALDI MS has great potential for the detection of small
molecules because of the absence of applied matrix. In this work,
a functionalized porous TiO2 film immobilized with gold
nanoparticles (AuNPs-FPTDF) was prepared to enhance SALDI MS performance.
The porous TiO2 films were prepared by the facile sol–gel
method and chemically functionalized for dense loading of AuNPs. The
prepared AuNPs-FPTDF showed superior performance in the detection
and imaging of small molecules in dual-polarity modes, with high detection
sensitivity in the low pmol range, good repeatability, and low background
noise compared to common organic MALDI matrixes. Its usage efficiently
enhanced SALDI MS detection of various small molecules, such as amino
acids and neurotransmitters, fatty acids, saccharides, alkaloids,
and flavonoids, as compared with α-cyano-4-hydroxycinnamic acid,
9-aminoacridine, and the three precursor substrates of AuNPs-FPTDF.
In addition, the blood glucose level in rats was successfully determined
from a linearity concentration range of 0.5–9 mM, as well as
other biomarkers in rat serum with SALDI MS. More importantly, the
spatial distribution of metabolites from the intact flowers of the
medicinal plant Catharanthus roseus was explored by using the AuNPs-FPTDF as an imprint SALDI MS substrate
in dual-polarity modes. These results demonstrate wide applications
and superior performances of the AuNPs-FPTDF as a multifunctional
SALDI surface with enhanced detection sensitivity and imaging capabilities.