I am a PhD student in Peter O'Connor's group based in the Ion Cyclotron Resonance Laboratory, Millburn House, Chemistry Department.
PhD Project - Detailed Structural Analysis of Singly Charged Agrochemicals via Advanced Mass Spectrometry Techniques
My PhD project is in collaboration with Syngenta and focuses on "Detailed Structural Analysis of Singly Charged Agrochemicals using Advanced Mass Spectrometry Techniques."
Structure elucidation is essential to ensure the correct target molecule has been synthesized and also supports the determination of any by-products and impurities that may have formed during synthesis. High-resolution accurate mass spectrometry has become the front-line tool for structural elucidation for agrochemicals and pharmaceuticals due to its ability to handle complex samples and characterize low-level components of interest. High mass accuracy and mass resolution allows reliable confirmation of elemental formula for precursor and product ions to interpret a spectrum and establish the structure. Elucidating the structure of a known molecule allows acquisition of a fingerprint spectrum of that molecule which can help in the elucidation of their respective metabolites. This is crucial for agrochemicals and drugs molecules, as their metabolites can be potentially toxic to humans, plants, and the environment.
Using different fragmentation techniques (such as collisionally activated dissociation (CAD/CID), infrared multiphoton dissociation (IRMPD), electron-induced dissociation (EID), and ultraviolet photodissociation (UVPD)) we investigate the fragmentation patterns of these species. We couple these fragmentation techniques and employ the advantages of two-dimensional mass spectrometry (2DMS) to aid with the structural analysis of complex mixtures.
2DMS has multiple benefits, such as it does not require chromatographic separation or quadrupole isolation of complex mixtures prior to analysis; 2DMS allows grouping of species that have common core structures or share functional groups. Furthermore, a single species can be used to calibrate the entire 2DMS spectrum to achieve sub-ppm to ppb mass accuracies on all species, known and unknown.
The application of 2DMS to the analyses of complex samples containing singly-charged agrochemicals and their metabolite compounds within environmentally relevant matrices is being assessed.
M. Sc. (Distinction) in Analytical Science & Instrumentation - The University of Warwick (2016-2017)
B.Sc. (Hons) in Chemistry - The University of Manchester (2011 – 2014)
The University of Warwick - Master's Project
Master’s Project - Supercharging Polymeric Molecules via a Novel Supercharging Source & Structure Elucidation of Oxidative Debris
The aim of the project was to supercharge polymeric molecules using a home-built supercharging source and the structure elucidation of oxidative debris.
The supercharging source, developed at Warwick University, uses a superacid (CH5+) to supercharge the molecule.
The University of Manchester - Mini Projects
Synthesis: Preparation of TADDOL Ligands: Applications of Asymmetric Catalysis
Synthesising TADDOL, via a two-step Grignard reaction, to be used as a chiral catalyst, in a titanium complex form, for the synthesis of an enantiomerically pure product via an asymmetric Diels-Alder reaction.
Measurement & Analytical: Zeolites and Solid State Characterisation Techniques
Synthesise zeolites and Mobil Composition of Matter (MCM). Characterise them via X-Ray Diffraction, Small Angle X-Ray Scattering, Scanning Electron Microscopy and Atomic Force Microscopy.
Computational: Environmental Speciation
Producing a model to fit experimental data; using the model to propose a mechanism to prevent nuclear waste contamination of a stream.
The University of Manchester, Chemical Engineering and Analytical Science
Analysing anti-bacterial coating on textiles via Solid Phase Micro-extraction Gas Chromatography-Mass Spectrometry and E-Nose.
The University of Manchester, Manchester Institute of Biotechnology
Dry work: Using COPASI to analyse the glycolysis mechanism in a yeast cell.
Investigate which enzyme(s) have the major effect on a single step in the model using the Metabolic Control Analysis (MCA) tool. Identify the flux at each step and minimised the flux for unwanted side reactions using information obtained from MCA.
Wet work: Ligation of yeast cells and DNA fragments for DNA molecular cloning.
University of Manchester, I.T. Department, Manchester Institute of Biotechnology
UPPCON 2018 - Leeds, UK (Poster Presentation)
BMSS SIG (AIMS) 2018 - Syngenta, Bracknell, UK
BMSS (2018) - Cambridge, UK (Poster Presentation)
BMSS (2019) - Manchester, UK (Oral Presentation)
ASMS (2020) - Virtual (Oral Presentation)
Syngenta Collaboration Conference (2020) - Virtual (Oral Presentation)
BMSS (2021) - Sheffield, UK (Poster Presentation)
Marzullo, B. P.; Morgan, T. E.; Wootton, C. A.; Li, M.; Perry, S. J.; Saeed, M.; Barrow, M. P.; O'Connor, P. B., Comparison of Fragmentation Techniques for the Structural Characterisation of Singly Charged Agrochemicals. Anal. Chem. 2020, 92 (4), 3143-3151.
Marzullo, B. P.; Morgan, T.; Wootton, C. A.; Perry, S. J.; Saeed, M.; Barrow, M. P.; O'Connor, P. B., The Advantages of Two-Dimensional Electron-Induced Dissociation and Infrared Multiphoton Dissociation Mass Spectrometry for the Analysis of Agrochemicals. Anal. Chem. 2020, 92 (17), 11687-11695.
Marzullo, B. P.; Morgan, T. E.; Theisen, A.; Haris, A.; Wootton, C. A.; Perry, S. J.; Saeed, M.; Barrow, M. P.; O’Connor, P. B., Combining Ultraviolet Photodissociation and Two-Dimensional Mass Spectrometry: A Contemporary Approach for Characterizing Singly Charged Agrochemicals. Anal. Chem. 2021, 93 (27), 9462-9470.
Morgan, T.; Wootton, C. A.; Marzullo, B. P.; Paris, J.; Kerr, A.; Ellacot, S. H.; van Agthoven, M. A.; Barrow, M. P.; Bristow, A. W. T.; Perrier, S.; O'Connor, P. B., Characterization across a dispersity: polymer mass spectrometry in the second dimension. J. Am. Soc. Mass Spectrom. 2021, 32 (8), 2153-2161.
Paris, J.; Morgan, T. E.; Marzullo, B. P.; Wootton, C. A.; Barrow, M. P.; O’Hara, J.; O’Connor, P. B., Two-Dimensional Mass Spectrometry Analysis of IgG1 Antibodies. J. Am. Soc. Mass Spectrom. 2021, 32 (7), 1716-1724.
Bryan Pietro Marzullo
MAS-CDT PhD (FT-ICR MS)
in collaboration with Syngenta.
E-Mail: b dot marzullo at warwick dot ac dot uk