The future is bright: Biofortification of common foods can improve vitamin D status.

Vitamin D deficiency is a global concern, linked to suboptimal musculoskeletal health and immune function, with status inadequacies owing to variations in UV dependent cutaneous synthesis and limited natural dietary sources. Endogenous biofortification, alongside traditional fortification and supplement usage is urgently needed to address this deficit. Evidence reviewed in the current article clearly demonstrates that feed modification and UV radiation, either independently or used in combination, effectively increases vitamin D content of primary produce or ingredients, albeit in the limited range of food vehicles tested to date (beef/pork/chicken/eggs/fish/bread/mushrooms). Fewer human trials have confirmed that consumption of these biofortified foods can increase circulating 25-hydroxyvitamin D [25(OH)D] concentrations (n = 10), which is of particular importance to avoid vitamin D status declining to nadir during wintertime. Meat is an unexplored yet plausible food vehicle for vitamin D biofortification, owing, at least in part, to its ubiquitous consumption pattern. Consumption of PUFA-enriched meat in human trials demonstrates efficacy (n = 4), lighting the way for exploration of vitamin D-biofortified meats to enhance consumer vitamin D status. Response to vitamin D-biofortified foods varies by food matrix, with vitamin D3-enriched animal-based foods observing the greatest effect in maintaining or elevating 25(OH)D concentrations. Generally, the efficacy of biofortification appears to vary dependent upon vitamer selected for animal feed supplementation (vitamin D2 or D3, or 25(OH)D), baseline participant status and the bioaccessibility from the food matrix. Further research in the form of robust human clinical trials are required to explore the contribution of biofortified foods to vitamin D status.

Evaluation of Chemcatcher® passive samplers for pesticide monitoring using high-frequency catchment scale data.

Passive samplers (PS) have been proposed as an enhanced water quality monitoring solution in rivers, but their performance against high-frequency data over the longer term has not been widely explored. This study compared the performance of Chemcatcher® passive sampling (PS) devices with high-frequency sampling (HFS: 7-hourly to daily) in two dynamic rivers over 16 months. The evaluation was based on the acid herbicides MCPA (2-methyl-4-chlorophenoxyacetic acid), mecoprop-P, fluroxypyr and triclopyr. The impact of river discharge parameters on Chemcatcher® device performance was also explored. Mixed effects modelling showed that time-weighted mean concentration (TWMC) and flow-weighted mean concentration (FWMC) values obtained by the HFS approach were both significantly higher (p < 0.001) than TWMC values determined from PS regardless of river or pesticide. Modelling also showed that TWMCPS values were more similar to TWMCHFS than FWMCHFS values. However, further testing revealed that MCPA TWMC values from HFS and PS were not significantly different (p > 0.05). There was little indication that river flow parameters altered PS performance-some minor effects were not significant or consistent. Despite this, the PS recovery of very low concentrations indicated that Chemcatcher® devices may be used to evaluate the presence/absence and magnitude of acid herbicides in hydrologically dynamic rivers in synoptic type surveys where space and time coverage is required. However, a period of calibration of the devices in each river would be necessary if they were intended to provide a quantitative review of pesticide concentration as compared with HFS approaches.

Vitamin D Biofortification of Pork May Offer a Food-Based Strategy to Increase Vitamin D Intakes in the UK Population.

Hypovitaminosis D is prevalent worldwide, with many populations failing to achieve the recommended nutrient intake (RNI) for vitamin D (10-20 µg/day). Owing to low vitamin D intakes, limited exposure to ultraviolet-B (UVB) induced dermal synthesis, lack of mandatory fortification and poor uptake in supplement advice, additional food-based strategies are warranted to enable the UK population to achieve optimal vitamin D intakes, thus reducing musculoskeletal risks or suboptimal immune functioning. The aims of the current study were to (1) determine any changes to vitamin D intake and status over a 9-year period, and (2) apply dietary modeling to predict the impact of vitamin D biofortification of pork and pork products on population intakes. Data from the UK National Diet and Nutrition Survey (Year 1-9; 2008/09-2016/17) were analyzed to explore nationally representative mean vitamin D intakes and 25-hydroxyvitamin D (25(OH)D) concentrations (n = 13,350). Four theoretical dietary scenarios of vitamin D pork biofortification were computed (vitamin D content +50/100/150/200% vs. standard). Vitamin D intake in the UK population has not changed significantly from 2008 to 2017 and in 2016/17, across all age groups, 13.2% were considered deficient [25(OH)D <25 nmol/L]. Theoretically, increasing vitamin D concentrations in biofortified pork by 50, 100, 150, and 200%, would increase vitamin population D intake by 4.9, 10.1, 15.0, and 19.8% respectively. When specifically considering the impact on gender and age, based on the last scenario, a greater relative change was observed in males (22.6%) vs. females (17.8%). The greatest relative change was observed amongst 11-18 year olds (25.2%). Vitamin D intakes have remained stable in the UK for almost a decade, confirming that strategies are urgently required to help the population achieve the RNI for vitamin D. Biofortification of pork meat provides a proof of concept, demonstrating that animal-based strategies may offer an important contribution to help to improve the vitamin D intakes of the UK population, particularly adolescents.

Approaches to herbicide (MCPA) pollution mitigation in drinking water source catchments using enhanced space and time monitoring.

Freshwater occurrences of the selective acid herbicide 2-methyl-4-chloro-phenoxyacetic acid (MCPA) are an ongoing regulatory and financial issue for water utility industries as the number and magnitude of detections increase, particularly in surface water catchments. Assessments for mitigating pesticide pollution in catchments used as drinking water sources require a combination of catchment-based and water treatment solutions, but approaches are limited by a lack of empirical data. In this study, an enhanced spatial (11 locations) and temporal (7-hourly to daily sampling) monitoring approach was employed to address these issues in an exemplar surface water source catchment (384 km2). The spatial sampling revealed that MCPA was widespread, with occurrences above the 0.1 µg L-1 threshold for a single pesticide being highly positively correlated to sub-catchments with higher proportions of 'Improved Grassland' land use (r = 0.84). These data provide a strong foundation for targeting catchment-based mitigation solutions and also add to the debate on the ecosystems services provided by such catchments. Additionally, of the 999 temporal samples taken over 12 months from the catchment outlet, 25% were above the drinking water threshold of 0.1 µg L-1. This prevalence of high concentrations presents costly problems for source water treatment. Using these data, abstraction shutdowns were simulated for five scenarios using hydrometeorological data to explore the potential to avoid intake of high MCPA concentrations. The scenarios stopped abstraction for 4.2-9.3% of the April-October period and reduced intake of water containing over 0.1 µg L-1 of MCPA by 16-31%. This represents an important development for real-time proxy assessments for water abstraction in the absence of more direct pesticide monitoring data.

Bacterial dioxygenase- and monooxygenase-catalysed sulfoxidation of benzo[b]thiophenes.

Asymmetric heteroatom oxidation of benzo[b]thiophenes to yield the corresponding sulfoxides was catalysed by toluene dioxygenase (TDO), naphthalene dioxygenase (NDO) and styrene monooxygenase (SMO) enzymes present in P. putida mutant and E. coli recombinant whole cells. TDO-catalysed oxidation yielded the relatively unstable benzo[b]thiophene sulfoxide; its dimerization, followed by dehydrogenation, resulted in the isolation of stable tetracyclic sulfoxides as minor products with cis-dihydrodiols being the dominant metabolites. SMO mainly catalysed the formation of enantioenriched benzo[b]thiophene sulfoxide and 2-methyl benzo[b]thiophene sulfoxides which racemized at ambient temperature. The barriers to pyramidal sulfur inversion of 2- and 3-methyl benzo[b]thiophene sulfoxide metabolites, obtained using TDO and NDO as biocatalysts, were found to be ca.: 25-27 kcal mol(-1). The absolute configurations of the benzo[b]thiophene sulfoxides were determined by ECD spectroscopy, X-ray crystallography and stereochemical correlation. A site-directed mutant E. coli strain containing an engineered form of NDO, was found to change the regioselectivity toward preferential oxidation of the thiophene ring rather than the benzene ring.

Enzyme-catalysed synthesis and reactions of benzene oxide/oxepine derivatives of methyl benzoates.

A series of twelve benzoate esters was metabolised, by species of the Phellinus genus of wood-rotting fungi, to yield the corresponding benzyl alcohol derivatives and eight salicylates. The isolation of a stable oxepine metabolite, from methyl benzoate, allied to evidence of the migration and retention of a carbomethoxy group (the NIH Shift), during enzyme-catalysed ortho-hydroxylation of alkyl benzoates to form salicylates, is consistent with a mechanism involving an initial arene epoxidation step. This mechanism was confirmed by the isolation of a remarkably stable, optically active, substituted benzene oxide metabolite of methyl 2-(trifluoromethyl)benzoate, which slowly converted into the racemic form. The arene oxide was found to undergo a cycloaddition reaction with 4-phenyl-1,2,4-triazoline-3,5-dione to yield a crystalline cycloadduct whose structure and racemic nature was established by X-ray crystallography. The metabolite was also found to undergo some novel benzene oxide reactions, including epoxidation to give an anti-diepoxide, base-catalysed hydrolysis to form a trans-dihydrodiol and acid-catalysed aromatisation to yield a salicylate derivative via the NIH Shift of a carbomethoxy group.

Methoxyl groups of plant pectin as a precursor of atmospheric methane: evidence from deuterium labelling studies.

* The observation that plants produce methane (CH4) under aerobic conditions has caused considerable controversy among the scientific community and the general public. It led to much discussion and debate not only about its contribution to the global CH4 budget but also about the authenticity of the observation itself. Previous results suggested that methoxyl groups of the abundant plant structural component pectin might play a key role in the in situ formation process of CH4. Here, this effect is investigated using an isotope labelling study. * Polysaccharides, pectin and polygalacturonic acid, with varying degrees of trideuterium-labelled methyl groups in the methoxyl moieties, were investigated for CH4 formation under UV irradiation and heating. * A strong deuterium signal in the emitted CH4 was observed from these labelled polysaccharides. * Results clearly demonstrate that ester methyl groups of pectin can serve as a precursor of CH4, supporting the idea of a novel chemical route of CH4 formation in plants under oxic environmental conditions.

Synthesis, structure and stereochemistry of quinoline alkaloids from Choisya ternata.

A range of seventeen quinoline alkaloids, involving several types of oxidations during their biosynthetic pathways, have been isolated from leaves of Choisya ternata. In addition to the nine known quinoline alkaloids, eight new members of the furoquinoline family, derived mainly from prenylation at C-5 (including two novel hydroperoxides), have been identified. The absolute configurations and enantiopurity values of all chiral quinoline alkaloids have been determined. One of the isolated alkaloids, 7-isopentenyloxy-gamma-fagarine, has been used as a precursor for the chemical asymmetric synthesis of the enantiopure alkaloids: evoxine, anhydroevoxine and evodine. The possible roles of oxygenase and other oxygen-atom-transfer enzymes, in the biosynthetic pathways of the C. ternata alkaloids, have been discussed.

A 19F NMR study of fluorobenzoate biodegradation by Sphingomonas sp. HB-1.

While several microorganisms readily degrade 2- and 4-fluorobenzoates, only a very small number appear to catabolise the 3-fluoro isomer, owing to the accumulation of toxic intermediates. Here we describe the isolation of a bacterium capable of using 3-fluorobenzoate as a sole source of carbon and energy, and the experiments conducted to define the steps involved in the biodegradation of this compound. The organism was identified as a strain belonging to the genus Sphingomonas by sequence analysis of its 16S rRNA gene. To date no other organism from this genus is known to degrade this compound. Using fluorine nuclear magnetic resonance spectroscopy (19F NMR) to analyse the culture supernatant it was possible to observe the disappearance of 3-fluorobenzoate and the appearance of fluoride ion and four other fluorinated compounds. These were identified as 3-fluorocatechol, 2-fluoromuconic acid and 3- and 5-fluoro-1,2-dihydro-1,2-dihydroxybenzoates. Thus, the likely catabolic pathway involves dioxygenation of 3-fluorobenzoate yielding fluorocatechol and subsequent intra-diol cleavage to yield fluoromuconic acid. The organism can also use 2- and 4-fluorobenzoates as growth substrates.

Chloride methylation by plant pectin: an efficient environmentally significant process.

Atmospheric chloromethane (CH3Cl) plays an important role in stratospheric ozone destruction, but many uncertainties exist regarding the strengths of its sources and sinks and particularly regarding the processes generating this naturally occurring gas. Evidence is presented here that CH3Cl is produced in many terrestrial environments by a common mechanism. Abiotic conversion of chloride to CH3Cl occurs readily in plant material, with the widespread plant component pectin acting as a methyl donor. Significant CH3Cl emissions from senescent and dead leaves were observed at ambient temperatures; those emissions rose dramatically when temperatures increased. This ubiquitous process acting in terrestrial ecosystems and during biomass burning could contribute the bulk of atmospheric CH3Cl.

Absolute configuration assignment and enantiopurity determination of chiral alkaloids and coumarins derived from O- and C-prenyl epoxides.

A combination method of ozonolysis and chiral stationary phase (CSP)-GC-MS analysis has been developed to determine the enantiopurity values and absolute configurations of a range of alkaloid and coumarin hemiterpenoids derived from C- and O-prenyl epoxides.

Identification of a phenolic 3-O-methyltransferase in the lignin-degrading fungus Phanerochaete chrysosporium.

A methyltransferase enzyme catalysing the 3-O-methylation of isovanillic acid (3-hydroxy-4-methoxybenzoic acid) by S-adenosylmethionine (SAM) was identified in Phanerochaete chrysosporium and purified. Gel filtration indicated an M(r) of 71,000 and SDS-PAGE showed that the enzyme was composed of two subunits of M(r) approximately 36,000. Substrate utilization studies demonstrated that the enzyme was highly specific, displaying an exclusive preference for the methylation of the 3-hydroxyl group of several substituted benzoic acids. 3-Hydroxybenzoic acids with a methoxyl or hydroxyl substituent in the 2 or 4 position were the best substrates with isovanillic and 3,4-dihydroxybenzoic acids showing the highest rates of methylation. The 3-O-methyltransferase enzyme was induced later in the growth cycle than the 4-O-methyltransferase previously isolated from this fungus, which is believed to have a role in the 4-O-methylation of lignin degradation products. However the function of this meta-specific enzyme, the first phenolic 3-O-methyltransferase isolated from a fungus, remains unclear. The combined activities of the 3- and 4-O-methyltransferase enzymes satisfactorily account for the pattern of SAM-dependent methylating activity shown by whole mycelia to phenolic substrates.