Browsing by Author "Percival, Benita"
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Item Metadata only Benchtop Low-Frequency 60 MHz NMR Analysis of Urine: A Comparative Metabolomics Investigation(MDPI, 2020-04-16) Leenders, Justine; Grootveld, Martin; Percival, Benita; Gibson, Miles; Casanova, Federico; Wilson, Philippe B.Metabolomics techniques are now applied in numerous fields, with the ability to provide information concerning a large number of metabolites from a single sample in a short timeframe. Although high-frequency (HF) nuclear magnetic resonance (NMR) analysis represents a common method of choice to perform such studies, few investigations employing low-frequency (LF) NMR spectrometers have yet been published. Herein, we apply and contrast LF and HF 1H-NMR metabolomics approaches to the study of urine samples collected from type 2 diabetic patients (T2D), and apply a comparative investigation with healthy controls. Additionally, we explore the capabilities of LF 1H-1H 2D correlation spectroscopy (COSY) experiments regarding the determination of metabolites, their resolution and associated analyses in human urine samples. T2D samples were readily distinguishable from controls, with several metabolites, particularly glucose, being associated with this distinction. Comparable results were obtained with HF and LF spectrometers. Linear correlation analyses were performed to derive relationships between the intensities of 1D and 2D resonances of several metabolites, and R2 values obtained were able to confirm these, an observation attesting to the validity of employing 2D LF experiments for future applications in metabolomics studies. Our data suggest that LF spectrometers may prove to be easy-to-use, compact and inexpensive tools to perform routine metabolomics analyses in laboratories and ‘point-of-care’ sites. Furthermore, the quality of 2D spectra obtained from these instruments in half an hour would broaden the horizon of their potential applications.Item Open Access Benchtop NMR Spectroscopy and Spectral Analysis of the cis- and trans-Stilbene Products of the Wittig Reaction(American Chemical Society, 2019-07-16) Edgar, Mark; Percival, Benita; Gibson, Miles; Masania, Jinit; Beresford, Ken; Wilson, Philippe B.; Grootveld, M.Benchtop NMR spectrometers are now becoming more widely employed in university teaching laboratories. These low-field instruments are increasingly used in reaction monitoring and product purity applications. NMR spectra obtained using these spectrometers (40–80 MHz) tend to suffer from significant overlap of signals when compared to those obtained at 300–400 MHz or above, and therefore, some reactions may be less suited to analysis using such benchtop systems. While some reactions can be modified to make them more amenable to analysis on low-field benchtop spectrometers, the fact remains that many common undergraduate laboratory chemistry reactions remain as a stalwart of the university education system. Therefore, there is currently a major requirement for benchtop NMR analysis to improve in order to facilitate student understanding. Herein, it is demonstrated that a combination of spectral analysis and simulation at low-fields (40–80 MHz) allows the fine structure of second-order effects and overlapping spectra to be deduced, enabling an improved understanding of the low-field benchtop NMR technique within undergraduate student cohorts. The evolution of well-resolved and distinct multiplets at 400 MHz to complex, overlapping multiplets at 40–80 MHz also serves as a useful guide for laboratory demonstrators and academic staff when explaining the advantages of such benchtop systems. The Wittig reaction has been a standard reaction practical session in many university teaching laboratories since the 1980s, the products of which are a mixture of cis- and trans-stilbenes. This reaction serves as an ideal example of how benchtop NMR spectrometers and analysis can support chemistry teaching laboratories.Item Metadata only Comparative 1H NMR-Based Chemometric Evaluations of the Time-Dependent Generation of Aldehydic Lipid Oxidation Products in Culinary Oils Exposed to Laboratory-Simulated Shallow Frying Episodes: Differential Patterns Observed for Omega-3 Fatty Acid-Containing Soybean Oils(MDPI, 2021-10-17) Wann, Angela; Percival, Benita; Woodason, Kate; Gibson, Miles; Vincent, Siany; Grootveld, MartinSoybean oil is the second most exported oil from the United States and South America, and is widely marketed as a cooking oil product containing numerous health benefits for human consumers. However, culinary oils with high polyunsaturated fatty acid (PUFA) contents, are known to produce high quantities of lipid oxidation products (LOPs), including toxic aldehydes upon exposure to high-temperature frying episodes. Previous studies have demonstrated causal links between aldehyde ingestion and inhalation with deleterious health perturbations, including mutagenic and carcinogenic effects, along with cardiovascular and teratogenic actions. In this study, aldehydic LOPs were detected and quantified in commercially available samples of soybean, avocado, corn and extra-virgin olive oil products before and after their exposure to laboratory-simulated laboratory frying episodes (LSSFEs) using high-resolution 1H nuclear magnetic resonance (NMR) analysis. Results acquired demonstrated that PUFA-rich soybean and corn oils gave rise to the highest concentrations of oil aldehydes from the thermo-oxidation of unsaturated fatty acids, whereas monounsaturated fatty acid (MUFA)-laden avocado and olive oils were much more resistant to this peroxidation process, as expected. Multivariate chemometrics analyses provided evidence that an orthogonal component pattern of aldehydic LOPs featuring low-molecular-mass n-alkanals such as propanal, and 4-oxo-alkanals, arises from thermo-oxidation of the ω-3 fatty acid (FA) linolenic acid (present in soybean oils at levels of ca. 7% (w/w)), was able to at least partially distinguish this oil from corresponding samples of thermally-stressed corn oil. Despite having a similar total PUFA level, corn oil has only a negligible ω-3 FA content, and therefore generated significantly lower levels of these two aldehyde classes. In view of the adverse health effects associated with dietary LOP ingestion, alternative methodologies for the incorporation of soybean oils within high-temperature frying practices are proposed.Item Metadata only Evaluations of the Peroxidative Susceptibilities of Cod Liver Oils by a 1H NMR Analysis Strategy: Peroxidative Resistivity of a Natural Collagenous and Biogenic Amine-Rich Fermented Product(MDPI, 2020-03-12) Percival, Benita; Wann, Angela; Zbasnik, Richard; Schelgel, Vicki; Edgar, Mark; Ampem, Gilbert; Le Gresley, Adam; Wilson, Philippe B.; Naughton, Declan; Grootveld, Martin; Zhang, JieHigh-resolution 1H nuclear magnetic resonance (NMR) analysis was employed to molecularly screen the lipid, lipid oxidation product (LOP), and antioxidant compositions of four natural (unrefined) cod liver oil (CLO) products. Products 1–3 were non-fermented CLOs, whilst Product 4 was isolated from pre-fermented cod livers. Supporting analytical data that were acquired included biogenic amine, flavanone, tannin, phenolic antioxidant, α-tocopherol, and oxygen radical absorbance capacity (ORAC) determinations by recommended HPLC, LC/MS/MS, or spectrophotometric methods. SDS-PAGE, HPLC, and 1H NMR analyses investigated and determined collagenous antioxidants and their molecular mass ranges. 1H NMR analysis of aldehydic LOPs was employed to explore the susceptibilities/resistivities of each CLO product to peroxidation that is induced by thermal stressing episodes (TSEs) at 180°C, or following prolonged (42 day) storage episodes at 4 and 23 °C. Product 4 displayed extremely high ORAC values, which were much greater than those of Products 1–3, and that were predominantly ascribable to significant levels of peroxidation-blocking and/or aldehyde-consuming collagenous polypeptides/peptides and ammoniacal agents therein. Significantly lower levels of toxic aldehydes were generated in the pre-fermented Product 4 during exposure to TSEs, or the above long-term storage episodes. These results confirmed the enhanced peroxidative resistivity of a fermented, antioxidant-fortified natural CLO product over those of non-fermented unrefined products. Product 4: Green Pasture Blue Ice™ Fermented Cod Liver Oil.Item Metadata only Extensive Chemometric Investigations of Distinctive Patterns and Levels of Biogenic Amines in Fermented Foods: Human Health Implications(MDPI, 2020-12-05) Grootveld, Martin; Percival, Benita; Zhang, JieAlthough biogenic amines (BAs) present in fermented foods exert important health-promoting and physiological function support roles, their excessive ingestion can give rise to deleterious toxicological effects. Therefore, here we have screened the BA contents and supporting food quality indices of a series of fermented food products using a multianalyte-chemometrics strategy. A liquid chromatographic triple quadrupole mass spectrometric (LC-MS/MS) technique was utilized for the simultaneous multicomponent analysis of 8 different BAs, and titratable acidity, pH, total lipid content, and thiobarbituric acid-reactive substances (TBARS) values were also determined. Rigorous univariate and multivariate (MV) chemometric data analysis strategies were employed to evaluate results acquired. Almost all foods analyzed had individual and total BA contents that were within recommended limits. The chemometrics methods applied were useful for recognizing characteristic patterns of BA analytes and food quality measures between some fermented food classes, and for assessing their inter-relationships and potential metabolic sources. MV analysis of constant sum-normalized BA profile data demonstrated characteristic signatures for cheese (cadaverine only), fermented cod liver oil (2-phenylethylamine, tyramine, and tryptamine), and wine/vinegar products (putrescine, spermidine, and spermine). In conclusion, this LC-MS/MS-linked chemometrics approach was valuable for (1) contrasting and distinguishing BA catabolite signatures between differing fermented foods, and (2) exploring and evaluating the health benefits and/or possible adverse public health risks of such products.Item Metadata only Low-Field Benchtop NMR Spectroscopy for Quantification of Aldehydic Lipid Oxidation Products in Culinary Oils during Shallow Frying Episodes(MDPI, 2023-03-15) Gibson, Miles; Percival, Benita; Edgar, Mark; Grootveld, MartinIntroduction: Toxic aldehydic lipid oxidation products (LOPs) arise from the thermo-oxidative deterioration of unsaturated fatty acids present in heated culinary oils when exposed to high-temperature frying episodes, and currently these effects represent a major public health concern. Objectives: In this study, we investigated the applications of low-field (LF), benchtop NMR analysis to detect and quantify toxic aldehyde species in culinary oils following their exposure to laboratory-simulated shallow frying episodes (LSSFEs) at 180 °C. Four culinary oils of variable fatty acid (FA) composition were investigated to determine the analytical capabilities of the LF NMR instrument. Oil samples were also analysed using a medium-field (400 MHz) NMR facility for comparative purposes. Results: Aldehydes were quantified as total saturated and total α,β-unsaturated classes. The time-dependent production of α,β-unsaturated aldehydes decreased in the order chia > rapeseed ≈ soybean > olive oils, as might be expected from their polyunsaturated and monounsaturated FA (PUFA and MUFA, respectively) contents. A similar but inequivalent trend was found for saturated aldehyde concentrations. These data strongly correlated with medium-field 1H NMR data obtained, although LF-determined levels were significantly lower in view of its inability to detect or quantify the more minor oxygenated aldehydic LOPs present. Lower limit of detection (LLOD) values for this spectrometer were 0.19 and 0.18 mmol/mol FA for n-hexanal and trans-2-octenal, respectively. Aldehydic lipid hydroperoxide precursors of aldehydic LOPs were also detectable in LF spectra. Conclusions: We therefore conclude that there is scope for application of these smaller, near-portable NMR facilities for commercial or ‘on-site’ quality control determination of toxic aldehydic LOPs in thermally stressed frying oils.Item Open Access New Developments in the NMR-Linked Metabolomics Analysis of Lysosomal Storage Disorders(De Montfort University, 2020-01) Percival, BenitaLysosomal storage disorders (LSDs) are predominantly rare, autosomal recessive, orphan diseases that impact the storage of specific molecules within the lysosome. This work explores current metabolomics research on LSDs with a specific focus on Niemann Pick Disease Type C, Gaucher’s Disease and Gangliosidoses. Moreover, metabolomic techniques are explored with a history and theory outlined for nuclear magnetic resonance (NMR) and liquid chromatography-mass spectrometric analytical strategies. Statistical analyses, particularly multivariate approaches, and machine learning applied to the analysis of these metabolomic datasets are also discussed. Human urinary and plasma metabolomics investigations were then performed using the 1H NMR technique on samples provided from Gaucher’s Disease and GM1 Type II patients with corresponding controls. Furthermore, using a feline model, a 1H NMR urinary investigation was performed to investigate the impact of Niemann Pick Disease Type C on the metabolome, and also to evaluate metabolic changes in felines treated with 2-hydroxypropyl-β-cyclodextrin. Statistical evaluations were performed for all three conditions, and the significance of these are highlighted, with some key potential biomarkers identified. The advantages of using a 1H NMR approach are summarised, in addition to the challenges of performing complex metabolomics analysis of LSDs, with particular considerations of the limited sample sizes of these available for such studies.Item Metadata only Potential Advantages of Peroxoborates and Their Ester Adducts Over Hydrogen Peroxide as Therapeutic Agents in Oral Healthcare Products: Chemical/Biochemical Reactivity Considerations In Vitro, Ex Vivo And In Vivo(MDPI, 2020-08-07) Grootveld, Martin; Lynch, Edward; Page, Georgina; Chan, W.; Percival, Benita; Anagnostaki, Eugenia; Mylona, Valina; Bordin-Aykroyd, Sonia; Grootveld, KerryPeroxides present in oral healthcare products generally exert favourable protective activities against the development and progression of tooth decay, plaque, gingivitis, and halitosis, etc. However, despite the high level of research focus on hydrogen and carbamide peroxides as therapeutically active (and tooth-whitening) agents, to date the use of alternative chemical forms of peroxides such as peroxoborates for these purposes has received only scant attention. Intriguingly, peroxoborate and its esters with polyols, such as glycerol, have a very diverse chemistry/biochemistry in aqueous solution, for which there is an increasing amount of evidence that it remains distinctive from that of hydrogen peroxide; such properties include self-associative and hydrolytic equilibria, and their abilities to participate in electrophile- or nucleophile-scavenging, metal ion-complexing, redox and free radical reactions, for example. Therefore, the purpose of this detailed commentary is to evaluate both differences and similarities between the molecular/biomolecular reactivities of peroxoborate species and hydrogen peroxide in vitro, ex-vivo and in vivo. It encompasses brief sectional accounts regarding the molecular heterogeneity of peroxoborates, the release of bioactive agents therefrom, and their oxidative attack on oral cavity biomolecules (the nucleophilic or electrophilic character of these oxidations are discussed). Further areas explored are the abilities of borates and peroxoborates to enhance the solubility of iron ions in aqueous solution, their involvements in free radical biochemistry (particularly the complexation of oxygen radical-promoting transition metal ions by, and antioxidant properties of, peroxoborate-polyol ester adducts), and the specific inhibition of protease enzymes. Further aspects focus on the tooth-whitening, oral malodor neutralizing, and potential mutagenic and genotoxic properties of peroxoborates, along with possible mechanisms for these processes. The abilities of peroxoborates, and peroxides in general, to modulate the activities of inflammatory mediators and vitamins, antioxidant or otherwise, are also explored.Item Metadata only Potential Adverse Public Health Effects Afforded by the Ingestion of Dietary Lipid Oxidation Product Toxins: Significance of Fried Food Sources(MDPI, 2020-04-01) Grootveld, Martin; Percival, Benita; Leenders, Justine; Wilson, Philippe B.Exposure of polyunsaturated fatty acid (PUFA)-rich culinary oils (COs) to high temperature frying practices generates high concentrations of cytotoxic and genotoxic lipid oxidation products (LOPs) via oxygen-fueled, recycling peroxidative bursts. These toxins, including aldehydes and epoxy-fatty acids, readily penetrate into fried foods and hence are available for human consumption; therefore, they may pose substantial health hazards. Although previous reports have claimed health benefits offered by the use of PUFA-laden COs for frying purposes, these may be erroneous in view of their failure to consider the negating adverse public health threats presented by food-transferable LOPs therein. When absorbed from the gastrointestinal (GI) system into the systemic circulation, such LOPs may significantly contribute to enhanced risks of chronic non-communicable diseases (NCDs), e.g. , cancer, along with cardiovascular and neurological diseases. Herein, we provide a comprehensive rationale relating to the public health threats posed by the dietary ingestion of LOPs in fried foods. We begin with an introduction to sequential lipid peroxidation processes, describing the noxious effects of LOP toxins generated therefrom. We continue to discuss GI system interactions, the metabolism and biotransformation of primary lipid hydroperoxide LOPs and their secondary products, and the toxicological properties of these agents, prior to providing a narrative on chemically-reactive, secondary aldehydic LOPs available for human ingestion. In view of a range of previous studies focused on their deleterious health effects in animal and cellular model systems, some emphasis is placed on the physiological fate of the more prevalent and toxic α,β-unsaturated aldehydes. We conclude with a description of targeted nutritional and interventional strategies, whilst highlighting the urgent and unmet clinical need for nutritional and epidemiological trials probing relationships between the incidence of NCDs, and the frequency and estimated quantities of dietary LOP intake.