Mark P Barrow

The University of Warwick · Department of Chemistry

There is a growing need to develop analytical methods that can distinguish compounds found within industrially derived oil sands process water (OSPW) from those derived from natural weathering of oil sands deposits. This is a difficult challenge as possible leakage beyond tailings pond containments will probably be in the form of mixtures of water-...

A new strategy has been developed for characterization of the most challenging complex mixtures to date, using a combination of custom-designed experiments and a new data pre-processing algorithm. In contrast to traditional methods, the approach enables operation of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with consta...

The use of hyphenated Fourier transform mass spectrometry (FTMS) methods affords additional information about complex chemical mixtures. Co-eluted components can be resolved thanks to the ultra-high resolving power, which also allows extracted ion chromatograms (EICs) to be used for the observation of isomers. As such datasets can be large and data...

The detailed molecular characterization of petroleum-related samples by mass spectrometry, often referred to as petroleomics, continues to present significant analytical challenges. As a result, petroleomics continues to be a driving force for the development of new ultrahigh resolution instrumentation, experimental methods, and data analysis proce...

High‐resolution mass spectrometry (HRMS) has become a vital tool for dissolved organic matter (DOM) characterization. The upward trend in HRMS analysis of DOM presents challenges in data comparison and interpretation among laboratories operating instruments with differing performance and user operating conditions. It is therefore essential that the...

Products of petroleum refining are substances that are both complex and variable. These substances are produced and distributed in high volumes; therefore, they are heavily scrutinized in terms of their potential hazards and risks. Because of inherent compositional complexity and variability, unique challenges exist in terms of their registration a...

Base oil is a main component of engine oil that enables smooth operation of an internal combustion engine. There are two types of base oils, such as mineral oil and synthetic oil. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and gas chromatography-mass spectrometry (GC-MS) were used to characterize the base...

Ultraviolet photodissociation is a fast, photon-mediated fragmentation method that yields high sequence coverage and informative cleavages of biomolecules. In this work, 193 nm UVPD was coupled with a 12 Tesla FT-ICR mass spectrometer and 10.6 μm infrared multi-photon dissociation to provide gentle slow-heating of UV-irradiated ions. No internal in...

Environmental pollution has strong links to adverse human health outcomes with risks of pollution through production, use, ineffective wastewater (WW) remediation, and/or leachate from landfill. ‘Fit-for-purpose’ monitoring approaches are critical for better pollution control and mitigation of harm, with current sample preparation methods for compl...

The composition of asphaltenes is of interest due to the challenges they pose for industry and their high complexity, encompassing a range of heteroatom contents, molecular weights, double bond equivalents (DBEs), and structural motifs. They are well-known for aggregating above critical concentrations, hindering the upstream and downstream processe...

The fine structure of isotopic peak distributions of glutathione in mass spectra is measured using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) at 12 and 15 T magnetic field, with an infinity cell and a dynamically harmonized cell (DHC) respectively. The resolved peaks in the fine structure of glutathione consist of 2H, 1...

Understanding modification of synthetic polymer structures is necessary for their accurate synthesis and potential applications. In this contribution, a series of partially hydrolyzed poly(2-oxazoline) species were produced forming poly[(2-polyoxazoline)-co-(ethylenimine)] (P(EtOx-co-EI)) copolymers; EI being the hydrolyzed product of Ox. Bulk mass...

Collisionally activated dissociation (CAD), infrared multiphoton dissociation (IRMPD), ultraviolet photodissociation (UVPD), electron capture dissociation and electron detachment dissociation (EDD) experiments were conducted on a set of phosphopeptides, in a Fourier transform ion cyclotron resonance mass spectrometer. The fragmentation patterns wer...

During the past decade, there has been sustained interest in papers published on naphthenic acids (NAs) and the broader class of naphthenic acid-fraction compounds (NAFCs) as part of environmental and petroleomic studies. This increase attention in part reflects that NAs and related NAFCs are principal toxicants in oil sands process-affected water...

Bio-oils are precursors for biofuels but are highly corrosive necessitating further upgrading. Furthermore, bio-oil samples are highly complex and represent a broad range of chemistries. They are complex mixtures not simply because of the large number of poly-oxygenated compounds but because each composition can comprise many isomers with multiple...

Sample preparation and instrument parameters have regularly been demonstrated to impact upon the observed results in atmospheric pressure photoionization, mass spectrometry (MS), and analytical techniques in general but may be overlooked when such methods are applied to the characterization of real-world samples. An initial investigation into diffe...

VKSim is open access, follow this link: https://kairos.warwick.ac.uk/VKSim/ Production of fuels and targeted chemicals from biomass represents a current challenge. Pyrolysis of biomass generates liquid bio-oils but these are highly complex mixtures. In order to obtain the desired...

Internal combustion engine lubricants are subject to thermo-oxidative degradation during use and must be designed to withstand oxidation in order to extend their useful life. Understanding the complex chemical process of thermo-oxidative degradation is essential to designing higher performing engine lubricants. In this study base oil samples compos...

Due to the natural dispersity that is present in synthetic polymers, an added complexity is always present in the analysis of polymeric species. Tandem mass spectrometry analysis requires the isolation of individual precursors before a fragmentation event to allow the unambiguous characterization of these species and is not viable at certain levels...

Two-dimensional mass spectrometry (2DMS) is a new, and theoretically ideal, data-independent analysis tool, which allows the characterization of a complex mixture and was used in the bottom-up analysis of IgG1 for the identification of post-translational modifications. The new peak picking algorithm allows the distinction between chimeric peaks in...

Marine heavy fuel oils (HFOs), derived from and often blended with hydrotreated residual cuts, typically possess high boiling point, viscosity, and molecular complexity, and so are inherently challenging to analyze at the molecular level. Their high asphaltene content is associated with undesirable phenomena including flocculation, deposition, and...

The structure and sequence elucidation of complex homo- and copolymers is key for further understanding polymers, polymer synthesis, and polymer interactions in biological processes. In this contribution, poly(dimethylacrylamide) homo- and dimethylacrylamide/4-acryloylmorpholine block copolymers were synthesized and analyzed by electron capture dis...

Deamidated amyloid proteins have been shown to accelerate fibril formation. Herein, the results show the inhibition performance and the interaction site between site-specific inhibitor and amyloid protein are significantly influenced...

Analysis of agrochemicals in an environmental matrix is challenging, due to these samples containing multiple agrochemicals, their metabolites, degradation products, and endogenous compounds. The analysis of such complex samples is achieved using chromatographic separation techniques coupled to mass spectrometry. Herein, we demonstrate a two-dimens...

Six essential oils were analyzed by Fourier transform ion cyclotron resonance mass spectrometry coupled to negative electrospray ionization (ESI(-)/FT-ICR MS). ESI offers selective ionization of compounds polar functional groups containing nitrogen and oxygen heteroatoms. ESI in negative-ion mode allows the identification of the acidic compounds. T...

The OsII arene anticancer complex [(η6-bip)Os(en)Cl]+ (Os1-Cl; where bip = biphenyl, and en = ethylenediamine) binds strongly to DNA1 and biomolecules. Here we investigate the interaction between Os1-Cl and the model protein, BSA using ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The specific bindin...

Amyloid fibril formation is a hallmark in a range of human diseases. Analysis of the molecular details of amyloid aggregation, however, is limited by the difficulties in solubilizing, separating, and identifying the aggregated biomolecules. Additional labeling or protein modification is required in many current analytical techniques in order to pro...

Investigating the structure of active ingredients, such as agrochemicals, and their associated metabolites, is a crucial requisite in the discovery and development of these molecules. In this study, structural characterisation by electron-induced dissociation (EID) was compared to collisionally activated dissociation (CAD) on a series of agrochemic...

In this work, a detailed analysis of a bio-oil obtained by pyrolysis of softwoods and its esterified product is described. Information of the type of chemical function groups were obtained by 13C and 1H nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) and compositional analysis was obtained by Fourier transform i...

In this work, a detailed analysis of a bio-oil obtained by pyrolysis of softwoods and its esterified product is described. Information of the type of chemical function groups were obtained by 13C and 1H nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) and compositional analysis was obtained by Fourier transform i...

Two-dimensional mass spectrometry (2D MS) is a data-independent tandem mass spectrometry technique in which precursor and fragment ion species can be correlated without the need for prior ion isolation. The behavior of phase in 2D Fourier transform mass spectrometry is investigated with respect to the calculation of phase-corrected absorption-mode...

Crude oil is among the most complex organic mixtures found in nature. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides the resolution and mass accuracy needed to analyze such complex mixtures. When mixtures contain many different components, a competitive effect within the ICR cell takes place that hampers the detect...

Two-dimensional mass spectrometry (2D MS) is a data-independent tandem mass spectrometry technique in which precursor and fragment ion species can be correlated without the need for prior ion isolation. The behavior of phase in 2D Fourier transform mass spectrometry is investigated with respect to the calculation of phase-corrected absorption-mode...

Native top-down mass spectrometry is a fast, robust biophysical technique that can provide molecular-scale information on the interaction between proteins or peptides and ligands, including metal cations. Here we have analyzed complexes of the full-length amyloid β (1-42) monomer with a range of (patho)physiologically relevant metal cations using n...

Native top-down mass spectrometry is a fast, robust biophysical technique that can provide molecular-scale information on the interaction between proteins or peptides and ligands, including metal cations. Here we have analyzed complexes of the full-length amyloid β (1-42) monomer with a range of (patho)physiologically relevant metal cations using n...

Considerable effort and progress has been made over the past decade with respect to development of analytical tools for the determination of naphthenic acids and related components in environmental samples. However, experimental variables that influence the analytical results have not been fully explored. The relative contributions of O x classes a...

Staten Island is located in one of the most densely populated regions of the US: the New York/New Jersey Estuary. Marine and industrial oil spills are commonplace in the area, causing the waterways and adjacent marshes to become polluted with a range of petroleum-related contaminants. Using Rock-Eval pyrolysis, the hydrocarbon impact on a salt mars...

The most widely used asnticancer drugs are platinum complexes, but complexes of other transition metals also show promise and may widen the spectrum of activity, reduce side-effects, and overcome resistance. The latter include organo-iridium(III) ‘piano-stool’ complexes. To understand their mechanism of action, it is important to discover how they...

Mass spectrometry has been applied to determine the deamidation sites and the aggregation region of the deamidated human islet amyloid polypeptide (hIAPP). Mutant hIAPP with iso-aspartic residue mutations at possible...

With increasing focus on the structural elucidation of polymers, advanced tandem mass spectrometry techniques will play a crucial role in the characterization of these compounds. In this contribution, synthesis and analysis of methyl initiated and xanthate terminated poly (2-ethyl-2-oxazoline) using Fourier transform ion cyclotron resonance (FT-ICR...

Two-dimensional mass spectrometry (2DMS) involves simultaneous acquisition of the fragmentation patterns of all the analytes in a mixture by correlating their precursor and fragment ions by modulating precursor ions systematically through a fragmentation zone. Tandem two-dimensional mass spectrometry (MS/2DMS) unites the ultra-high accuracy of Four...

Two-dimensional Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (2D FT-ICR MS or 2D MS) allows data independent fragmentation of all ions in a sample, and correlation of fragment ions to their precursors without isolation prior to fragmentation. Developments in computer capabilities and implementations in FTMS over of the last decade ha...

Octahedral platinum(IV) complexes such as trans,trans,trans-[Pt(N3)2(OH)2(pyridine)2] (1) are stable in the dark, but potently cytotoxic to a range of cancer cells when activated by UVA or visible light, and active in vivo. Photoactivation causes the reduction of the complex and leads to the formation of unusual Pt(II) lesions on DNA. However, radi...

Two-dimensional mass spectrometry (2D MS) correlates precursor and fragment ions without ion isolation in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) for tandem mass spectrometry. Infrared activated electron capture dissociation (IR-ECD), using a hollow cathode configuration, generally yields more information for pepti...

Fourier transform ion cyclotron resonance mass spectrometry affords the resolving power to determine an unprecedented number of components in complex mixtures, such as petroleum. The software tools required to also analyze these data struggle to keep pace with advancing instrument capabilities and increasing quantities of data, particularly in term...

Two-dimensional mass spectrometry (2D MS) is a tandem mass spectrometry technique that allows data-independent fragmentation of all precursors in a mixture without previous isolation, through modulation of the ion cyclotron frequency in the ICR-cell prior to fragmentation. Its power as an analytical technique has been proven particularly for proteo...

Two-Dimensional Fourier transform ion cyclotron resonance mass spectrometry (2D FT-ICR MS or 2D MS) allows direct correlation between precursor and fragment ions without isolation prior to fragmentation. The method has been optimised for the analysis of complex mixtures, and used so far for the analysis of small molecules, peptides obtained by tryp...

Transition metal-based proteins and enzymes are critical for the maintenance of cellular function and metal-based (metallo)drugs are commonly used for the treatment of many diseases, such as cancer. Detection and characterisation of metallodrug targets is crucial for improving drug-design and therapeutic efficacy. Due to the unique isotopic ratios...

The analysis of petrochemical materials and particulate matter originating from combustion sources remains a challenging task for instrumental analytical techniques. A detailed chemical characterisation is essential for addressing health and environmental effects. Sophisticated instrumentation, such as mass spectrometry coupled with chromatographic...

Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry (2D FT-ICR MS) allows data-independent fragmentation of all ions in a sample and correlation of fragment ions to their precursors through the modulation of precursor ion cyclotron radii prior to fragmentation. Previous results show that implementation of 2D FT-ICR MS with i...

Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry (2D FT-ICR MS) allows the correlation between precursor and fragment ions in tandem mass spectrometry without the need to isolate the precursor ion beforehand. 2D FT-ICR MS has been optimized as a data-independent method for the structural analysis of compounds in complex s...

A complementary study, using FTICR-MS and solid-state NMR, shows a high degree of polymorphism exhibited by Aβ species in forming hydrogen-bonded networks. Two Alzheimer’s Aβ peptides selectively labeled with 17O and 15N were investigated. Using 15N{17O}REAPDOR solid-state NMR, the peptides involved in forming hydrogen bond were determined, while t...

The forensic studies of naphthenic acids fraction components in oil sands process water (OSPW) and crude oil has continued to receive significant attention due to increased need to explicate the toxicological claims of these components and their distributions in environmental samples and to address the problems faced in the petroleum industry. The...

The forensic studies of naphthenic acids fraction components in oil sands process water (OSPW) and crude oil has continued to receive significant attention due to increased need to explicate the toxicological claims of these components and their distributions in environmental samples and to address the problems faced in the petroleum industry. The...

Mass spectrometry can be used to determine structural information about ions by activating precursors and analysing the resulting series of fragments. Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry (2D FT-ICR MS) is a technique that correlates the mass-to-charge (m/z) ratio of fragment and precursor ions in a single spe...

A comparison of the acidic and basic extracts of oil sands process water (OSPW) was performed using positive-and negative-ion electrospray ionization (ESI) and atmospheric pressure photoionization (APPI), coupled with a 12 T solariX Fourier transform ion cyclotron resonance mass spectrometer (FTICR MS). In general, the acid-neutral extracts showed...

Background Recent experimental evidence suggests that nitric oxide (NO) and hydrogen sulfide signaling pathways are intimately intertwined particularly in the vasculature, with mutual attenuation or potentiation of biological responses under control of the soluble guanylyl cyclase (sGC) / phopshodiesterase (PDE) pathway. There is now compelling evi...

Significance Reactions of sulfur-centered nucleophiles with nitrogenous species have been studied independently for more than a century for synthetic/industrial purposes; to understand geochemical, atmospheric, and biological processes; and to explain the origins of life. Various products and reaction mechanisms were proposed. We here identify a si...

Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry is a data-independent analytical method that records the fragmentation patterns of all the compounds in a sample. This study shows the implementation of atmospheric pressure photoionization with two-dimensional (2D) Fourier transform ion cyclotron resonance mass spectrometr...

There is a growing need for environmental screening of natural waters in the Athabasca region of Alberta, Canada, particularly in the differentiation between anthropogenic and naturally-derived organic compounds associated with weathered bitumen deposits. Previous research has focused primarily upon characterization of naphthenic acids in water sam...

There has been a recent surge in the development of mass spectrometric methods for detailed characterization of naphthenic acid fraction compounds (all Cc Hh Nn Oo Ss , species, including heteroatomic and aromatic components in the acid-extractable fraction) in environmental samples. This surge is driven by the increased activity in oil sands envir...

The Os(II) arene anticancer complex [(η(6)-bip)Os(en)Cl](+) (Os1-Cl; where bip = biphenyl, and en = ethylenediamine) binds strongly to DNA. Here we investigate reactions between Os1-Cl and the self-complementary 12-mer oligonucleotide 5'-TAGTAATTACTA-3' (DNA12) using ultra high resolution Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry...

Deamidation is a non-enzymatic post-translational modification of asparagine to aspartic acid or glutamine to glutamic acid, converting an uncharged amino acid to a negatively charged residue. It is plausible that deamidation of asparagine and glutamine residues would result in disruption of a proteins' hydrogen bonding network and thus lead to pro...