Diamond nanoparticles (DNPs) were incorporated into matrix-assisted laser desorption/ionization (MALDI) samples to enhance the sensitivity of the mass spectrometer to carbohydrates. The DNPs optimize the MALDI sample morphology and thermalize the samples for thermally labile compounds because they have a high thermal conductivity, a low extinction coefficient in UV-vis spectral range, and stable chemical properties. The best enhancement effect was achieved when matrix, DNP, and carbohydrate solutions were deposited and vacuum-dried consecutively to form a trilayer sample morphology. It allows the direct identification of underivatized carbohydrates mixed with equal amount of proteins because no increase in the ion abundance of proteins was achieved. For dextran with an average molecular weight of 1500, the trilayer method typically improves the sensitivity by 79- and 7-fold in comparison to the conventional dried-droplet and thin-layer methods, respectively.
Abstract. This work demonstrates a method to prepare homogeneous distributions of analytes to improve data reproducibility in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS). Natural-air drying processes normally result in unwanted heterogeneous spatial distributions of analytes in MALDI crystals and make quantitative analysis difficult. This study demonstrates that inducing Marangoni flows within drying droplets can significantly reduce the heterogeneity problem. The Marangoni flows are accelerated by changing substrate temperatures to create temperature gradients across droplets. Such hydrodynamic flows are analyzed semi-empirically. Using imaging mass spectrometry, changes of heterogeneity of molecules with the change of substrate temperature during drying processes are demonstrated. The observed heterogeneities of the biomolecules reduce as predicted Marangoni velocities increase. In comparison to conventional methods, drying droplets on a 5°C substrate while keeping the surroundings at ambient conditions typically reduces the heterogeneity of biomolecular ions by 65%-80%. The observation suggests that decreasing substrate temperature during droplet drying processes is a simple and effective means to reduce analyte heterogeneity for quantitative applications.
A method for the rapid screening and determination of amphetamine-type designer drugs in saliva by a novel nib-assisted paper spray-mass spectrometry procedure is described. Under optimized conditions, the limit of detections for amphetamine derivatives (model samples: o-, m-, p-chloroamphetamine and o-, m-, p-fluoroamphetamine, respectively) were determined to 0.1 μg/mL by the nib-assisted paper spray-mass spectrometry method. This method is easier and has a higher sensitivity than similar methodologies, including atmospheric pressure/matrix-assisted laser desorption ionization mass spectrometry and electrospray-assisted laser desorption ionization/mass spectrometry. Data obtained using more classical separation methods, including liquid chromatography and capillary electrophoresis, are also reported.
A novel drug-screening system, consisting of paper spray-MS (PS-MS) and a CE-ESI-MS method was developed. This system can be easily switched either to PS-MS for rapidly screening samples or to the traditional CE-ESI-MS method for separation and to obtain detailed mass spectral information, while sharing the same mass spectrometer. In the former case, when a sharp (15°-tip) chromatography paper was used, the optimized distance from the paper tip to the mass inlet was 7.7 mm, whereas the optimized distance for the CE-ESI tip was ∼13.5 mm. Using 4-chloroamphetamine as a model compound, the LODs for PS-MS and CE-ESI-MS were determined to ∼0.1 and 0.25 ppm, respectively. Comparisons of results obtained using PS-MS and CE-ESI-MS and the experimental conditions are described.
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