Desorption atmospheric pressure photoionization
Desorption atmospheric pressure photoionization (DAPPI) is an ambient ionization technique for mass spectrometry that uses hot solvent vapor for desorption in conjunction with photoionization. Ambient Ionization techniques allow for direct analysis of samples without pretreatment. The direct analysis technique, such as DAPPI, eliminates the extraction steps seen in most nontraditional samples. DAPPI can be used to analyze bulkier samples, such as, tablets, powders, resins, plants, and tissues. The first step of this technique utilizes a jet of hot solvent vapor. The hot jet thermally desorbs the sample from a surface. The vaporized sample is then ionized by the vacuum ultraviolet light and consequently sampled into a mass spectrometer. DAPPI can detect a range of both polar and non-polar compounds, but is most sensitive when analyzing neutral or non-polar compounds. This technique also offers a selective and soft ionization for highly conjugated compounds.
The history of desorption atmospheric pressure photoionization is relatively new, but can be traced back through developments of ambient ionization techniques dating back to the 1970s. DAPPI is a combination of popular techniques, such as, atmospheric pressure photoionziation (APPI) and surface desorption techniques. The photoionization techniques were first developed in the late 1970s and began being used in atmospheric pressure experiments in the mid 1980s. Early developments in the desorption of open surface and free matrix experiements were first reported in literature in 1999 in an experiment using desorption/ionization on silicon (DIOS). DAPPI replaced techniques such as desorption electrospray ionization (DESI) and direct analysis in real time (DART). This generation of techniques are all recent developments seen in the 21st century. DESI was discovered in 2004 at Purdue University, while DART was discovered in 2005 by Laramee and Cody. DAPPI was developed soon after in 2007 at the University of Helsinki, Finland. The development of DAPPI widened the range of detection for nonpolar compounds and added a new dimension of thermal desorption of direct analysis samples.
The first operation to occur during desorption atmospheric pressure photoionization is desorption. Desorption of the sample is initiated by a hot jet of solvent vapor that is targeted onto the sample by a nebulizer microchip. The nebulizer microchip is a glass device bonded together by pyrex wafers with flow channels embedded from a nozzle at the edge of the chip. The microchip is heated to 250-350C in order to vaporize the entering solvent and create dopant molecules. Dopant molecules are added to help facilitate the ionization of the sample. Some of the common solvents include: nitrogen, toluene, acetone, and anisole. The desorption process can occur by two mechanisms: thermal desorption or momentum transfer/liquid spray. Thermal desorption uses heat to volatilize the sample and increase the surface temperature of the substrate. As the substrate's surface temperature is increased, the higher the sensitivity of the instrument. While studying the substrate temperature, it was seen that the solvent did not have a noticeable effect on the final temperature or heat rate of the substrate. Momentum transfer or liquid spray desoprtion is based on the solvent interaction with the sample, causing the release of specific ions. The momentum transfer is propagated by the collision of the solvent with the sample along with the transfer of ions with the sample. The transfer of positive ions, such as protons and charge transfers, are seen with the solvents: toluene and anisole. Toluene goes through a charge exchange mechanism with the sample, while acetone promotes a proton transfer mechanism with the sample. A beam of 10 eV photons that are given off by a UV lamp is directed at the newly desorbed molecules, as well as the dopant molecules. Photoionization then occurs, which knocks out the molecule's electron and produces an ion. This technique alone is not highly efficient for different varieties of molecules, particularly those that are not easily protonated or deprotonated. In order to completely ionize samples, dopant molecules must help. The gaseous solvent can also undergo photoionization and act as an intermediate for ionization of the sample molecules. Once dopant ions are formed, proton transfer can occur with the sample, creating more sample ions. The ions are then sent to the mass analyzer for analysis.
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