High-pressure mass spectrometry has been employed to investigate hydrogen and sodium bound ion-molecule complexes in the gas phase. Insight into the structure and reactivity of ion-molecule complexes has been gained by examining simple mono-ketones of butanone and 2-pentanone and more complex β-diketones of 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione. The effect of fluorinating 2,4-pentanedione exhibits experimental trends that are not representative of current electronic structure calculations . A novel method of sodium ion production has been developed using sodium metal, allowing for equilibrium measurements below 150 °C. Sodium containing ion-molecule complexes have been investigated using the new method of sodium ion production.

High-pressure mass spectrometry has been employed to investigate hydrogen and sodium bound ion-molecule complexes in the gas phase. Insight into the structure and reactivity of ion-molecule complexes has been gained by examining simple mono-ketones of butanone and 2-pentanone and more complex β-diketones of 2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione. The effect of fluorinating 2,4-pentanedione exhibits experimental trends that are not representative of current electronic structure calculations . A novel method of sodium ion production has been developed using sodium metal, allowing for equilibrium measurements below 150 °C. Sodium containing ion-molecule complexes have been investigated using the new method of sodium ion production.

A growing interest in the strengths of several interactions that play important structural roles in biochemical systems has been building over the past couple decades. The binding energies and entropies of formation of the clusters of several protonated amino acids and nucleic acid bases with methanol have been measured using High Pressure Mass Spectrometry. The results generally show that binding energy decreases when the proton affinity difference between the alcohol and amino acid is increased. The structures and energies of various alcohol stabilized conformers of these protonated biomolecules were computed using ab initio calculations at the MP2(Full)/6‐311++g(2d,2p) level of theory. The enthalpies of formation of the lowest energy conformers of the proton‐bound clusters between the alcohols and amino acids or peptides match very closely with the experimental values, indicating that protonation and subsequent methanol attachment occurs primarily at the terminal amine functionality. The methanol stabilized protonated nucleic acid bases have energies that match closely with a more entropically favourable conformation of the cluster, hence yielding less negative enthalpy changes experimentally. The effect of alcohol size on binding energy was also monitored through measurements of enthalpies and entropies of formation for the clusters of protonated diglycine with several alcohols. The binding energy between protonated diglycine and benzene was also measured, yielding a measurable cation‐π interaction of over 20 kcal mol‐1, a comparable value to typical strong hydrogen bonds.

A growing interest in the strengths of several interactions that play important structural roles in biochemical systems has been building over the past couple decades. The binding energies and entropies of formation of the clusters of several protonated amino acids and nucleic acid bases with methanol have been measured using High Pressure Mass Spectrometry. The results generally show that binding energy decreases when the proton affinity difference between the alcohol and amino acid is increased. The structures and energies of various alcohol stabilized conformers of these protonated biomolecules were computed using ab initio calculations at the MP2(Full)/6‐311++g(2d,2p) level of theory. The enthalpies of formation of the lowest energy conformers of the proton‐bound clusters between the alcohols and amino acids or peptides match very closely with the experimental values, indicating that protonation and subsequent methanol attachment occurs primarily at the terminal amine functionality. The methanol stabilized protonated nucleic acid bases have energies that match closely with a more entropically favourable conformation of the cluster, hence yielding less negative enthalpy changes experimentally. The effect of alcohol size on binding energy was also monitored through measurements of enthalpies and entropies of formation for the clusters of protonated diglycine with several alcohols. The binding energy between protonated diglycine and benzene was also measured, yielding a measurable cation‐π interaction of over 20 kcal mol‐1, a comparable value to typical strong hydrogen bonds.

Gunshot residue (GSR) analysis is a crucial aspect of the investigation of firearms-related incidents. The presence of GSR on a person or surface can provide valuable insight regarding proximity or involvement of an individual in a shooting incident. Traditionally, GSR analysis relies on the detection of inorganic compounds within the ammunition, known as inorganic gunshot residue (IGSR). These inorganic compounds are comprised of lead, barium, and antimony. IGSR compounds originate from the content of the primer, and each individual element is expelled during discharge, fused while molten, and land on nearby surfaces. Stubs with an adhesive coat are used to collect these particles by pressing against a surface suspected to have GSR particles. The current analytical method for detection and identification of IGSR, Scanning Electron Microscopy and Energy Dispersive X-Ray Spectroscopy (SEM/EDS), surveys GSR stubs for both the elemental composition as well as the morphology of the compounds. Positive identification requires both the elemental composition and spherical morphology of IGSR. Several issues exist with the nature of IGSR as well as the current method of analysis. Identification by SEM/EDS not only requires time for transportation and labor but may also produce false negatives due to inconsistent shape or lack of all three elements. The development of a rapid and robust analytical technique would address these deficiencies. Mass spectrometry (MS) is a standard analytical technique known for its specificity and accuracy. New advancements in research and technology have produced the ability to miniaturize MS while retaining its superior capabilities in identification. The characteristics of IGSR also pose issues in terms of validity, such as specificity to discharging a weapon, and ability to be transferred or wiped off. Qualities such as these can lead to both false negatives and false positives. In recent years, advances in forensic science research have studied the composition of organic gunshot residue (OGSR) as well as new methods for detecting these compounds. Research has pointed towards advantages in OGSR that would rectify the analytical issues seen in using IGSR as the target compound. Some qualities of OGSR that would improve GSR detection are its specificity to GSR, the molecular complexity of its components, its higher persistence on surfaces, and lower transferability. This study addressed both issues by employing the MX908 High Pressure Mass Spectrometer and developing an analytical method for major OGSR targets. The objective of this research was to test the MX908’s ability to ionize and detect Nitroglycerin (NG), Diphenylamine (DPA), Ethyl Centralite (EC), Dibutyl Phthalate (DBP), and Nitroguanidine (NQ). Furthermore, these experiments tested a range of voltage parameters to achieve optimal fragmentation, and ultimately an accurate and specific analytical method.

Mass-selected infrared multiple photon spectroscopy (IRMPD), Fourier transform ion cyclotron resonance (FT-ICR) kinetic experiments, RRKM and electronic structure calculations have been performed in order to propose a complex mechanism involving the formation of the proton-bound dimer of water (H5O2+) from 1,1,3,3-tetrafluorodimethyl ether. It has been found that the reaction is facilitated by a series of sequential exothermic bimolecular ion-molecule reactions. Evidence for the dominant mechanistic pathway involving the reaction of CF2H-O=CHF+, an ion of m/z 99, with water is presented. The primary channel occurs via nucleophilic attack of water on the ion of m/z 99 (CF2H-O=CHF+), to lose formyl fluoride and yield protonated difluoromethanol (m/z 69). Association of a second water molecule with protonated difluoromethanol generates a reactive intermediate which decomposes via a 1,4-elimination to release hydrogen fluoride and yield the proton-bound dimer of water and formyl fluoride (m/z 67). The 1,4-elimination of hydrogen fluoride is found to be strongly supported by the results of both RRKM theory and electronic structure calculations. Lastly, the elimination of formyl fluoride occurs by the association of a third water molecule to produce H5O2+ (m/z 37). The most probable isomeric forms of the ions with m/z 99 and 69 were found using IRMPD spectroscopy and electronic structure theory calculations. Thermochemical information for reactant, transition and product species was obtained using MP2/aug-cc-pVQZ//MP2(full)/6-31G(d) level of theory. Ionic hydrogen bond (IHB) interactions, resulting from the association of ammonia and two of the protonated methylxanthine derivatives, caffeine and theophylline, have been characterized using mass-selected IRMPD and electronic structure calculations at the MP2/aug-cc-pVTZ//B3LYP/6-311+G(d,p) level of theory. It was found that the formation of a proton-bound dimer (PBD) of caffeine and ammonia was elusive under the experimental conditions. The low binding energy of the caffeine and ammonia PBD is responsible for the perceived difficulty in obtaining an IRMPD spectrum. The IRMPD spectrum of the PBD of theophylline and ammonia was obtained and revealed bidentate IHB formation within the complex, which greatly increased the binding energy relative to the most stable isomer of the PBD of caffeine and ammonia. The IRMPD spectra of the protonated forms of caffeine and theophylline have also obtained. The spectrum of protonated caffeine showed the dominant existence of a single isomer, whereas the spectrum of protonated theophylline showed a mixture of isomers. The mixture of isomers of protonated theophylline resulted as a consequence of proton-transport catalysis (PTC) occurring within the PBD of theophylline and ammonia. All calculated harmonic spectra have been produced at the B3LYP/6-311+G(d,p) level of theory with fundamental frequencies scaled by 0.9679; calculated anharmonic spectra have also been provided at the same level of theory and were found to greatly improve the match with the IRMPD spectra obtained in all cases. Ionic hydrogen bond (IHB) interactions, resulting from the association of caffeine and theophylline with their protonated counterparts, forming proton-bound homodimers, have been characterized using mass-selected IRMPD and electronic structure calculations at the MP2/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory. It is found that the IRMPD spectra of the proton-bound homodimers of caffeine and theophylline are complicated resulting from the existence of several pairs of enantiomers separated by a narrow range of relative Gibbs free energies (298 K) of 15.6 and 18.2 kJ mol-1, respectively. The IRMPD spectrum of the proton-bound homodimer of theophylline is dominated by a unique isomer facilitated by formation of a bidentate IHB. Formation of this interaction lowers the relative Gibbs free energy of the ion to 9.75 kJ mol-1 below that of the most favourable pair of enantiomers. The IRMPD spectrum of the PBD of caffeine is complicated by the existence of at least two pairs of enantiomers with the strong likelihood of the spectral contributions of a third pair existing. The most favourable enantiomeric pair involves the formation of a O-H+⋯O IHB. However, verification of a pair of enantiomeric PBDs containing a N-H+⋯O IHB is also observed in the IRMPD spectrum of the PBD of caffeine due to the presence of three free carbonyl stretching modes located at 1731, 1751 and 1785 cm-1. The mass-selected IRMPD spectra of the sodium cation-bound dimers (SCBD) of caffeine and theophylline also have been obtained. Both the mass-selected IRMPD spectra and electronic structure calculations predict the most likely structure of the SCBDs of caffeine and theophylline to form by an efficient O⋯Na+⋯O interaction between C=O functional groups possessed by each monomer. The frequencies of the C=O-Na+ stretch are found to be nearly identical in the IRMPD spectra for both of the SCBDs of caffeine and theophylline at 1644 and 1646 cm-1, respectively. However, the degenerate free C=O symmetric and asymmetric stretches for the SCBDs of caffeine and theophylline found at 1732 and 1758 cm^(-1), respectively, demonstrating a red-shift for caffeine possibly linked to a steric interaction absent in theophylline. Free rotation about the O⋯Na+⋯O bond is found to greatly decrease the complexity of the IRMPD spectra of the SCBDs of caffeine and theophylline and demonstrates excellent agreement between the IRMPD and calculated spectra. Electronic structure calculations have been done at the MP2(full)/aug-cc-pCVTZ/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory using the aug-cc-pCVTZ basis set for Na+ and all Na+-interacting heterotatoms, and the 6-311+G(2d,2p) basis set for all non-interacting atoms within the SCBDs, in order to provide accurate electronic energies. Currently, installation and implementation of a pulsed electrospray high pressure ion source mated to an existing high pressure mass spectrometer (HPMS) is underway. The new ion source will greatly increase the range of possibilities for the study of ion-molecule reactions in the McMahon laboratory. One of the unique features of the new design is the incorporation of a gas-tight electrospray interface, allowing for more possibilities than only the study of cluster-ion equilibria involving hydration (H2On⋯S+), where S+ is an ion produced by electrospray. Other small prototypical biological molecules such as amines and thiols can be used without concern for the toxicity of these species. Another unique design feature allows electrosprayed ions to associate with neutral solvent species in an electric field free reaction chamber (RC). This ensures that values of equilibrium constants determined are truly representative of ions in states of thermochemical equilibrium. The existing HPMS in the McMahon laboratory is limited to the study of small volatile organic molecules. The new ion source will permit the exploration of systems involving non-volatile species, doubly charged ions and many biologically relevant molecules such as amino acids, peptides, nucleobases and carbohydrates.

Mass-selected infrared multiple photon spectroscopy (IRMPD), Fourier transform ion cyclotron resonance (FT-ICR) kinetic experiments, RRKM and electronic structure calculations have been performed in order to propose a complex mechanism involving the formation of the proton-bound dimer of water (H5O2+) from 1,1,3,3-tetrafluorodimethyl ether. It has been found that the reaction is facilitated by a series of sequential exothermic bimolecular ion-molecule reactions. Evidence for the dominant mechanistic pathway involving the reaction of CF2H-O=CHF+, an ion of m/z 99, with water is presented. The primary channel occurs via nucleophilic attack of water on the ion of m/z 99 (CF2H-O=CHF+), to lose formyl fluoride and yield protonated difluoromethanol (m/z 69). Association of a second water molecule with protonated difluoromethanol generates a reactive intermediate which decomposes via a 1,4-elimination to release hydrogen fluoride and yield the proton-bound dimer of water and formyl fluoride (m/z 67). The 1,4-elimination of hydrogen fluoride is found to be strongly supported by the results of both RRKM theory and electronic structure calculations. Lastly, the elimination of formyl fluoride occurs by the association of a third water molecule to produce H5O2+ (m/z 37). The most probable isomeric forms of the ions with m/z 99 and 69 were found using IRMPD spectroscopy and electronic structure theory calculations. Thermochemical information for reactant, transition and product species was obtained using MP2/aug-cc-pVQZ//MP2(full)/6-31G(d) level of theory. Ionic hydrogen bond (IHB) interactions, resulting from the association of ammonia and two of the protonated methylxanthine derivatives, caffeine and theophylline, have been characterized using mass-selected IRMPD and electronic structure calculations at the MP2/aug-cc-pVTZ//B3LYP/6-311+G(d,p) level of theory. It was found that the formation of a proton-bound dimer (PBD) of caffeine and ammonia was elusive under the experimental conditions. The low binding energy of the caffeine and ammonia PBD is responsible for the perceived difficulty in obtaining an IRMPD spectrum. The IRMPD spectrum of the PBD of theophylline and ammonia was obtained and revealed bidentate IHB formation within the complex, which greatly increased the binding energy relative to the most stable isomer of the PBD of caffeine and ammonia. The IRMPD spectra of the protonated forms of caffeine and theophylline have also obtained. The spectrum of protonated caffeine showed the dominant existence of a single isomer, whereas the spectrum of protonated theophylline showed a mixture of isomers. The mixture of isomers of protonated theophylline resulted as a consequence of proton-transport catalysis (PTC) occurring within the PBD of theophylline and ammonia. All calculated harmonic spectra have been produced at the B3LYP/6-311+G(d,p) level of theory with fundamental frequencies scaled by 0.9679; calculated anharmonic spectra have also been provided at the same level of theory and were found to greatly improve the match with the IRMPD spectra obtained in all cases. Ionic hydrogen bond (IHB) interactions, resulting from the association of caffeine and theophylline with their protonated counterparts, forming proton-bound homodimers, have been characterized using mass-selected IRMPD and electronic structure calculations at the MP2/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory. It is found that the IRMPD spectra of the proton-bound homodimers of caffeine and theophylline are complicated resulting from the existence of several pairs of enantiomers separated by a narrow range of relative Gibbs free energies (298 K) of 15.6 and 18.2 kJ mol-1, respectively. The IRMPD spectrum of the proton-bound homodimer of theophylline is dominated by a unique isomer facilitated by formation of a bidentate IHB. Formation of this interaction lowers the relative Gibbs free energy of the ion to 9.75 kJ mol-1 below that of the most favourable pair of enantiomers. The IRMPD spectrum of the PBD of caffeine is complicated by the existence of at least two pairs of enantiomers with the strong likelihood of the spectral contributions of a third pair existing. The most favourable enantiomeric pair involves the formation of a O-H+⋯O IHB. However, verification of a pair of enantiomeric PBDs containing a N-H+⋯O IHB is also observed in the IRMPD spectrum of the PBD of caffeine due to the presence of three free carbonyl stretching modes located at 1731, 1751 and 1785 cm-1. The mass-selected IRMPD spectra of the sodium cation-bound dimers (SCBD) of caffeine and theophylline also have been obtained. Both the mass-selected IRMPD spectra and electronic structure calculations predict the most likely structure of the SCBDs of caffeine and theophylline to form by an efficient O⋯Na+⋯O interaction between C=O functional groups possessed by each monomer. The frequencies of the C=O-Na+ stretch are found to be nearly identical in the IRMPD spectra for both of the SCBDs of caffeine and theophylline at 1644 and 1646 cm-1, respectively. However, the degenerate free C=O symmetric and asymmetric stretches for the SCBDs of caffeine and theophylline found at 1732 and 1758 cm^(-1), respectively, demonstrating a red-shift for caffeine possibly linked to a steric interaction absent in theophylline. Free rotation about the O⋯Na+⋯O bond is found to greatly decrease the complexity of the IRMPD spectra of the SCBDs of caffeine and theophylline and demonstrates excellent agreement between the IRMPD and calculated spectra. Electronic structure calculations have been done at the MP2(full)/aug-cc-pCVTZ/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory using the aug-cc-pCVTZ basis set for Na+ and all Na+-interacting heterotatoms, and the 6-311+G(2d,2p) basis set for all non-interacting atoms within the SCBDs, in order to provide accurate electronic energies. Currently, installation and implementation of a pulsed electrospray high pressure ion source mated to an existing high pressure mass spectrometer (HPMS) is underway. The new ion source will greatly increase the range of possibilities for the study of ion-molecule reactions in the McMahon laboratory. One of the unique features of the new design is the incorporation of a gas-tight electrospray interface, allowing for more possibilities than only the study of cluster-ion equilibria involving hydration (H2On⋯S+), where S+ is an ion produced by electrospray. Other small prototypical biological molecules such as amines and thiols can be used without concern for the toxicity of these species. Another unique design feature allows electrosprayed ions to associate with neutral solvent species in an electric field free reaction chamber (RC). This ensures that values of equilibrium constants determined are truly representative of ions in states of thermochemical equilibrium. The existing HPMS in the McMahon laboratory is limited to the study of small volatile organic molecules. The new ion source will permit the exploration of systems involving non-volatile species, doubly charged ions and many biologically relevant molecules such as amino acids, peptides, nucleobases and carbohydrates.