Depth-Dependent Chemical Analysis of Handwriting by Nanospray Desorption Electrospray Ionization Mass Spectrometry.

Nanospray desorption electrospray ionization (nano-DESI) has been utilized in direct sampling mass spectrometry (MS) that requires highly spatially resolved sampling with minimal sample destruction. In this study, we explored the applicability of nano-DESI MS for the forensic chemical analysis of ink directly from handwriting on paper. Nano-DESI readily ionizes dyes, including the polyanionic ones, with minimal fragmentation and produces chemical fingerprints of ballpoint pens directly from a paper surface. Further, we specifically focused on how the potential of nano-DESI that changes the mass spectral profiles over time could reflect the differential distribution of analytes in a vertical direction because mildly extracted analytes are immediately transferred and analyzed in real time. To test this, we wrote the character "X" with various combinations of two different pens and analyzed the crosspoints by nano-DESI MS. As a result, the time-course changes in the chemical fingerprints of the ink, which were consistent with the order of the pen strokes, were successfully obtained by nano-DESI MS in most cases. After confirming the capability of the depth-dependent analysis of nano-DESI MS, we analyzed a simulated forgery in which the original and forged writings were made before and after affixing a seal and clearly distinguished the two portions based on the time-dependent changes in the profile of the ink compound.

Direct analysis of triacylglycerols from crude lipid mixtures by gold nanoparticle-assisted laser desorption/ionization mass spectrometry.

Triacylglycerols (TAGs), essential energy storage lipids, are easily detected by conventional MALDI MS when occurring on their own. However, their signals are easily overwhelmed by other lipids, mainly phosphatidylcholines (PCs) and, therefore, require purification. In order to profile TAGs from crude lipid mixtures without prefractionation, we investigated alternative matrixes that can suppress phospholipid ion signals and enhance cationization of TAGs. We found that an aqueous solution of citrate-capped gold nanoparticles (AuNPs) with a diameter of 12 nm is a superior matrix for the laser desorption/ionization mass spectrometry (LDI MS) of TAGs in crude lipid mixtures. The AuNP matrix effectively suppressed other lipid signals such as phospholipids and also provided 100 times lower detection limit for TAGs than 2,5-dihydroxybenzoic acid (DHB), the best conventional MALDI matrix for TAGs. The AuNP-assisted LDI MS enabled us to obtain detailed TAG profiles including minor species directly from crude beef lipid extracts without phospholipid interference. In addition, we could detect TAGs at a trace level from a total brain lipid extract.