Adam Cismesia




Office: CLB302



University of Florida
Ph.D. in Analytical Chemistry, 2013-2018
Graduate Research Project with Dr. Nick Polfer
IRMPD Spectroscopy, Mass Spectrometry and Instrumentation Development


Purdue University
B.S. Chemistry, Dec 2012.
Undergraduate Research with Hilkka Kenttämaa: Characterization of Asphaltenes Using Tandem Mass Spectrometery


Research Interests:

I am interested in instrumentation development and biomolecular applications using infrared multiple photon dissocaiton (IRMPD) spectroscopy and mass spectrometery. Over the past four years, my primary focus has been on the development of a cryogenic, mass-selective 2D ion trap that will allow us to utilize infrared predissociation spectroscopy (IRPD) for the structural elucidation of metabolites. In the current field of metabolomics – the study of small molecules (metabolites) which are products or byproducts of cellular processes – two main methods are used to identify unknown metabolites: Nuclear magnetic resonance (NMR) and liquid chromatography tandem mass spectrometry (LC-MS/MS). Both techniques have their strengths and weaknesses: NMR is the gold standard in terms of molecular identification, but its low sensitivity makes it difficult to probe low-abundance features in biological samples; conversely, LC-MS/MS has excellent sensitivity, but identification is limited to previously cataloged MS/MS spectra in databases. The application of IRPD to metabolite identification will introduce a new dimension of structural information for unknown analytes detected by MS. The high-resolution IR spectra of cryogenically cooled ions is expected to allow a chemical classification of unknown analytes based on diagnostic vibrations.



The development of a mass spectrometer that would operate at cryogenic temperatures involved a fundamental understanding of how mass spectrometers work, as well as how to use both a computer aided design (CAD) program (SolidWorksTM) and an ion simulation program (SIMIONTM). Although specific details about the ion trap and new instrumentation (including both CAD and real time images) can’t be shown here until publication, however a cartoon version of the trap along with the IRMPD instrumentation can be seen below. 


Our initial experiments, which involved using a neutral tagging agent (N2) were not very successful which we believe was due to initial temperature constraints and inefficient cooling methods. But out of this handicap, we found that due to the cool source conditions of our ESI source, we were able to isolate and utilize solvent tagging (ACN & H2O) as a method to probe the IR spectrum of an analyte (in our case metabolites). Furthermore, this new trap allows for the ability to multiplex or obtain multiple IR spectra simultaneously allowing this method to be more analytically useful (see below). This data was recently published and is described in more detail here. We are now working on applying this tagging method to isomeric/isobaric metabolites and fundamentally studying how these solvent tags affect the IR spectrum. We also have had a recent success in using N2 as a tagging method which is currently undergoing fundamental and analytical studies and will be displayed here once published as part of our new instrument paper.



I was also involved with two other projects that were both recently published. The first, which was my own work, involved the use of vibrational ion spectroscopy and computational chemistry to investigate the protonation sites of the positional isomers (ortho-, meta-, and para-) of aminobenzoic acid in the gas phase. By visual comparison of the vibrational ion spectra obtained by infrared multiple photon dissociation (IRMPD) spectroscopy, it is clear that the vibrational modes differ based on substituent position. Utilizing density functional theory (DFT) level calculations, it was determined that para-aminobenzoic acid (PABA) is protonated on the carboxylic acid site, whereas meta-aminobenzoic acid (MABA) is protonated on the amine. Ortho-aminobenzoic acid (OABA) is predicted to be protonated on the amine, in agreement with the IRMPD spectrum and computed thermochemistry, even if the proximity of the amino and acid groups make this a more special case for a sharing of the proton.


The second was that of my former group member, Amanda Patrick, in which I assisted in the study of how both source temperature and the choice of electrospray ionization (ESI) solvent affected the protonation site of para-aminobenzoic acid.



Please click on pdf link for Adam's cv.


Please click on pdf link for Adam's résumé




'Making Mass Spectrometry See the Light: The Promises and Challenges of Cryogenic Infrared Ion Spectroscopy as a Bioanalytical Technique', AP Cismesia, LS Bailey, MR Bell, LF Tesler, NC Polfer; J. Am. Soc. Mass Spectrom., 2016.


'Effects of ESI conditions on kinetic trapping of the solution-phase protonation isomer of p-aminobenzoic acid in the gas phase', AL Patrick, AP Cismesia, LF Tesler, NC Polfer; Int. J. Mass. Spectrom., 2017.


'Amine vs. carboxylic acid protonation in ortho-, meta-, and para-aminobenzoic acid: An IRMPD spectroscopy study', AP Cismesia, GR Nicholls, NC Polfer; J. Molec. Spectroscopy, 2017.


'Infrared ion spectroscopy inside a mass-selective cryogenic 2D linear ion trap', AP Cismesia, LF Tesler, MR Bell, LS Bailey, NC Polfer; J. Mass Spectrom., 2017.



Adam's LinkedIn Page