Rapid
analysis of phosphopeptides and phospholipids in biological
matrixes is of significant interest in multiple disciplines of life
sciences. Herein, trace phospholipids in human plasma, whole blood,
and undiluted human urine as well as phosphopeptides in protein digest
were selectively captured on a homemade array of TiO2 nanowires
for sensitive characterization by internal extractive electrospray
ionization mass spectrometry (TiO2-iEESI-MS). Sequential
release of captured chemicals from TiO2 array was achieved
by tuning pH of the extraction solvent. A single sample analysis,
including sample loading, chemical extraction and MS detection, was
accomplished within 3 min. As far as the quantification of phospholipids,
acceptable linearity (R
2 ≥ 0.9985)
and relative standard deviations (RSDs ≤ 8.9%) were obtained
within the range of 0.1–500 μg L–1 for
LysoPC(14:0) and LysoPC(16:0) in raw urine samples. Limit of detection
(LOD) ≤ 0.025 μg L–1 and recovery rates
of 94.8–101.6% were obtained for these phospholipids. As far
as the quantification of phosphopeptides, R
2 ≥ 0.9994 and RSDs ≤ 9.2% within the range of 0.3–200
μg L–1 were obtained for two phosphopeptides
in nonphosphopeptides mixtures. LODs ≤ 0.09 μg L–1 and recovery rates of 83.4–107.0% were obtained
for these phosphopeptides. On the basis of the orthogonal partial
least-squares discriminant analysis, TiO2-iEESI-MS patterns
from the blood of 46 patients with ovarian cancer were confidently
discriminated from the MS patterns of 46 healthy volunteers. Our results
indicate the strong potential of TiO2-iEESI-MS approach
for the selective detection of trace phosphopeptides and phospholipids
in various biological matrixes with high sensitivity, high specificity,
low sample consumption, and high throughput.