Search

BackgroundGiven the recent detection of tetrodotoxin (TTX) in bivalve molluscs but the absence of a full collaborative validation study for TTX determination in a large number of shellfish samples, interlaboratory assessment of method performance was required to better understand current capabilities for accurate and reproducible TTX quantitation using chemical and immunoassay methods.ObjectiveThe aim was to conduct an interlaboratory study with multiple laboratories, using results to assess method performance and acceptability of different TTX testing methods.MethodsHomogenous and stable mussel and oyster materials were assessed by participants using a range of published and in-house detection methods to determine mean TTX concentrations. Data were used to calculate recoveries, repeatability, and reproducibility, together with participant acceptability z-scores.ResultsMethod performance characteristics were good, showing excellent sensitivity, recovery, and repeatability. Acceptable reproducibility was evidenced by HorRat values for all LC–MS/MS and ELISA methods being less than the 2.0 limit of acceptability. Method differences between the LC–MS/MS participants did not result in statistically different results. Method performance characteristics compared well with previously published single-laboratory validated methods and no statistical difference was found in results returned by ELISA in comparison with LC–MS/MS.ConclusionThe results from this study demonstrate that current LC–MS/MS methods and ELISA are on the whole capable of sensitive, accurate, and reproducible TTX quantitation in shellfish. Further work is recommended to expand the number of laboratories testing ELISA and to standardize an LC–MS/MS protocol to further improve interlaboratory precision.HighlightsMultiple mass spectrometric methods and a commercial ELISA have been successfully assessed through an interlaboratory study, demonstrating excellent performance.

Relative colour constancy is an essential requirement for many scientific imaging applications. However, most digital cameras differ in their image formations and native sensor output is usually inaccessible, e.g., in smartphone camera applications. This makes it hard to achieve consistent colour assessment across a range of devices, and that undermines the performance of computer vision algorithms. To resolve this issue, we propose a colour alignment model that considers the camera image formation as a black-box and formulates colour alignment as a three-step process: camera response calibration, response linearisation, and colour matching. The proposed model works with non-standard colour references, i.e., colour patches without knowing the true colour values, by utilising a novel balance-of-linear-distances feature. It is equivalent to determining the camera parameters through an unsupervised process. It also works with a minimum number of corresponding colour patches across the images to be colour aligned to deliver the applicable processing. Two challenging image datasets collected by multiple cameras under various illumination and exposure conditions were used to evaluate the model. Performance benchmarks demonstrated that our model achieved superior performance compared to other popular and state-of-the-art methods., Comment: 14 pages, 8 figures, 2 tables, accepted by IEEE Transactions on Image Processing

Bacterial pathogens represent a safety concern in the food industry, and this is amplified by the lack of sensing devices that can be applied on-site by non-trained personnel. In this study, peroxidase-mimicking activity of gold nanostars was exploited to develop a user-friendly colourimetric sensor. A smartphone was exploited as an image reader and analyser, empowered with a novel App developed in-house. The mobile App was evaluated and compared with a commercial smartphone App for its capability to quantify generated colourimetric signals. A major obstacle found with sensors relying on gold nanozymes is the fact that modification of the surface of gold nanoparticles with biorecognition elements generally lead to a suppression of their nanozyme activity. This drawback was overcome by introducing an autocatalytic growth step, which successfully restored the peroxidase-mimicking activity through generation of new gold nanoseeds acting as catalytic centres. A proof-of-concept using this sensing mechanism was developed targeting Mycobacterium bovis, a zoonotic pathogen primarily found in cattle but that can be transmitted to humans by consumption of contaminated food and cause tuberculosis disease. The resulting smartphone-based immunological sensor has shown promising results with a linear response between 104 – 106 CFU/mL, enabling detection of M. bovis at concentrations as low as 7.2·103 CFU/mL in buffer conditions. It is anticipated that the concept of the developed approach will have applicability in many fields relying on smartphone-based biosensing.

Various 2-substituted-1,3-dithiane oxides (1-oxide and 1,3-dioxide) have been metalated and reacted for the first time with a trialkylborane (trioctylborane). The 2-chloro-1,3-dioxide results in migration of an octyl group from boron to carbon with the displacement of chloride and gives nonanoic acid after oxidation, but there is no evidence for a second migration involving displacement of a sulfenate group. The reaction involving lithiation of the 2-methoxy-1-oxide results in two migrations, with the displacement of both the methoxy group and the thiolate unit of the dithiane ring, giving dioctyl ketone after oxidation, but the yield is low, primarily because thiophilic addition of the lithiating agent predominates over lithiation. Again, there is no evidence for the displacement of the sulfenate unit. However, the intermediate prior to oxidation can be treated with trifluoroacetic anhydride to induce a Pummerer rearrangement, and the presumed trifluoroacetoxyalkylthiolate group then acts as a novel leaving group and is displaced, resulting in trioctylmethanol on oxidation, but the yield is again very low.

Despite the centrality of staple grains for human well-being, both as a source of nutrients and of toxic ions, there is little understanding of where and how elements vary, and if there are particular elements that correlate. Here, for shop bought polished (white) rice, we comprehensively characterized trace (arsenic species, cadmium, copper, iron, manganese, molybdenum, rubidium and zinc) and macro-nutrients (calcium, chlorine, potassium, phosphorus and sulphur) for grain purchased in 18 countries, across four continents, a total of 1045 samples. This was to investigate if there were any major differences between geographic location and elemental content, and to observe if there were any patterns in elemental distribution. Greatest variation in the median was observed for the non-essential rubidium (15-fold) and arsenic species (fivefold). Rubidium was the highest in the Americas, lowest in Europe, while inorganic arsenic (iAs) and dimethylarsonic acid (DMA) were low for Africa and high in the South American and European continents. The highest concentrations of cadmium were found in Asian samples, and lowest in South America, with variation within these regions. At the extremes of individual counties, China had fivefold higher concentrations than the global median, while Tanzania was fourfold lower than this value. Calcium, potassium, molybdenum and phosphorus were the highest in European and lowest in African grain, though the fold-differences were relatively low, ~ 0.2, while iron was the highest in African grain and lowest in European, Asian and South American grain, with a ~ twofold difference. Selenium was also higher in Africa versus other regions, and copper, manganese and zinc were the highest in American grain. Factor analysis showed that copper, cadmium, molybdenum, rubidium and selenium were strongly associated together, and these element’s factor loadings were diametrically opposed to less tightly associated calcium, chlorine, manganese, potassium, phosphorus and sulphur. Stepwise additions linear region analysis was performed on log-transformed concentrations to investigate cadmium associations in more detail. Selenium was the greatest predictor of cadmium concentration, followed by molybdenum, accounting for over 50% of the contribution to the adjusted R2. Arsenic species were only weakly correlated with other elements. The implications for these findings with respect to dietary nutrition are discussed. Vietnamese rice was notable in being deficient in macro- and micro-nutrients while also being elevated in cadmium at a median of 0.02 mg/kg, with China though still having a median that is ~ 2.5-fold this concentration. These Chinese concentrations are of particular concern as the 75th percentile for China is 0.1 mg/kg, a value that triggers regulatory action for rice products.

Studies of a catalytic asymmetric version of the Matteson reaction between dichloromethylboronates and organolithium reagents have been undertaken. From several different chiral catalytic systems studied, only one based on a mannitol derivative has given substantial asymmetric induction close to that previously achieved with a bis(oxazoline) derivative and ytterbium triflate. More detailed study of the latter reaction revealed that fresh ytterbium triflate actually reduced the level of asymmetric induction, while "aged" ytterbium triflate, or a fresh sample that had been treated with water, brought about improved induction. The implications of these findings are discussed.

Due to complex, valuable, and often extremely opaque supply chains, seafood is a commodity that has experienced a high prevalence of food fraud throughout the entirety of its logistics network. Fraud detection and prevention require an in-depth understanding of food supply chains and their vulnerabilities and risks so that food business operators, regulators, and other stakeholders can implement practical countermeasures. An analysis of historical criminality within a sector, product, or country is an important component and has not yet been conducted for the seafood sector. This study examines reported seafood fraud incidents from the European Union's Rapid Alert System for Food and Feed, Decernis's Food Fraud Database, HorizonScan, and LexisNexis databases between January 01, 2010 and December 31, 2020. Illegal or unauthorized veterinary residues were found to be the most significant issue of concern, with most reports originating from farmed seafood in Vietnam, China, and India. For internationally traded goods, border inspections revealed a significant frequency of reports with fraudulent or insufficient documentation, indicating that deceptive practices are picked up at import or export but are occurring further down the supply chain. Practices such as species adulteration (excluding veterinary residues), species substitution, fishery substitution, catch method fraud, and illegal, unreported, and unregulated fishing were less prevalent in the databases than evidenced in the scientific literature. The analysis demonstrates significant differences in outcomes depending on source and underlines a requirement for a standardized and rigorous dataset through which food fraud can be scrutinized to ensure enforcement, as well as industry and research resources are directed accurately. Practical Application: Levels of historic food fraud in a product, sector, supply chain node or geographic location provide an indication of historic criminality, the methods used and the location of reported frauds. This study provides an overview of historic levels of seafood fraud that can be used to inform seafood fraud prevention and mitigation activities by the food industry, regulators and other stakeholders.

Despite the centrality of staple grains for human well-being, both as a source of nutrients and of toxic ions, there is little understanding of where and how elements vary, and if there are particular elements that correlate. Here, for shop bought polished (white) rice we comprehensively characterize trace (arsenic species, cadmium, copper, iron, manganese, molybdenum, rubidium and zinc) and macro-nutrients (calcium, chlorine, potassium, phosphorus and sulphur) for grain purchased in 18 countries, across 4 continents, a total of 1045 samples, to investigate if there were any major differences between geographic location and elemental content, and to observe if there were any patterns in elemental distribution. Greatest variation in the median was observed for the non-essential rubidium (15-fold) and arsenic species (5-fold). Rubidium was highest in the Americas, lowest in Europe, while inorganic arsenic and dimethylarsonic acid (DMA) were low for Africa and high in the South American and European continents. Cadmium had the highest concentration in Asian samples and lowest in South America. Calcium, potassium, molybdenum and phosphorus, were highest in European and lowest in African grain, though the fold-differences were relatively low, ~ 0.2, while iron was highest in African grain and low in European, Asian and South American grain, with a ~ 2-fold difference. Selenium was also higher in Africa versus other regions, and copper, manganese and zinc where highest in American grain. Factor analysis showed that copper, cadmium, molybdenum, rubidium and selenium were strongly associated together, and these element’s factor loadings were diametrically opposed to less tightly associated calcium, chlorine, manganese, potassium, phosphorus and sulphur. Stepwise additions linear region analysis was performed on log transformed concentrations to investigate cadmium associations in more detail. Selenium was the greatest predictor of cadmium concentration, followed by molybdenum, accounting for over 50% of the contribution to the adjusted R2. Arsenic species were only weakly correlated with other elements. The implications for these findings with respect to dietary nutrition are discussed.

Fish is an excellent source for high-quality protein, good fat (omega 3 and 6), vitamin (B, D), and minerals (Ca, P, Zn, I, Mg, K, etc.) and can lower blood pressure and help reduce the risk of a heart attack or stroke. The illegal addition of formaldehyde (FA) to extend the shelf life is a common problem reported in many countries and the FA is classified as a group 1 human carcinogen by the International Agency for Research on Cancer (IARC). There is also the natural formation pathway of FA in fish and seafood. This article summarises the FA levels in fish and seafood (from 2000), formation pathways, health risk assessment, regulations, and analytical techniques to measure FA. It is shown that the reported FA levels are frequently higher than the recognised safety level of 5 mg/kg. This review highlights the requirement of a broad scale effort to measure the indigenous FA levels in fish and ensure that this can be differentiated by the illegal addition of FA. This will allow the strengthening of regulations and allow monitoring to detect and deter the practice of illegal addition of FA to fish and seafood.

Botulinum neurotoxins (BoNTs) are notorious toxins and powerful agents and can be lethal, causing botulism, but they are also widely used as therapeutics, particularly to treat neuromuscular disorders. As of today, the commercial BoNT treatments available are from native A or B serotypes. Serotype F has shown efficacy in a clinical trial but has scarcely been used, most likely due to its medium duration of effect. Previously, the uniqueness of the light chain of the F7 subtype was identified and reported, showing an extended interaction with its substrates, VAMPs 1, 2 and 3, and a superior catalytic activity compared to other BoNT/F subtypes. In order to more extensively study the properties of this neurotoxin, we engineered a modified F7 chimera, mrBoNT/F7-1, in which all the regions of the neurotoxin were identical to BoNT/F7 except the activation loop, which was the activation loop from BoNT/F1. Use of the activation loop from BoNT/F1 allowed easier post-translational proteolytic activation of the recombinant protein without otherwise affecting its properties. mrBoNT/F7-1 was expressed, purified and then tested in a suite of in vitro and in vivo assays. mrBoNT/F7-1 was active and showed enhanced potency in comparison to both native and recombinant BoNT/F1. Additionally, the safety profile remained comparable to BoNT/F1 despite the increased potency. This new modified recombinant toxin F7 could be further exploited to develop unique therapeutics to address unmet medical needs.

Organic food fraud is a significant challenge in the food testing sector—high price premiums, ease of access to produce to be relabelled and difficulties in developing testing strategies that can detect such frauds make organic foods particularly attractive and thus highly vulnerable to fraud. Samples of conventional and organic cattle taken across meat plants in Ireland and the United Kingdom, consisting of the neck (supraspinatus), rump (gluteus), and shin (flexor carpi radialis) regions of the carcass were analysed using a high resolution time-of-flight based rapid evaporative ionisation mass spectrometry (REIMS) system. The resulting untargeted lipidomic data (m/z 600–1000) was used to generate PCA-LDA models for production system and for muscle type, for these models, it was found that the production system model could differentiate organic from conventional beef with an accuracy of 84%, whilst the muscle type model could identify the cut of meat with a 98% accuracy; additionally, samples can be assessed against multiple models simultaneously, reducing analysis time and sample numbers. The use of REIMS showed considerable promise in its ability to detect different forms of meat fraud; its accuracy in differentiating organic from conventional beef is superior to stable isotope ratio mass spectrometry, with the added advantages of substantially shorter analysis times and lower sample analysis costs. The ability to rapidly confirm the cut of meat also demonstrates the potential of REIMS to concurrently determine multiple aspects of beef authenticity in a close to real time analysis.

Various methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes have been used as regioselectivity modifiers in the chlorination reactions of various phenols at room temperature. The process involves the use of a slight excess of sulfuryl chloride in the presence of aluminum or ferric chloride as an activator. Methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes having 2 and 3 methylene groups as a spacer were found to be good for the para-selective chlorination of o-cresol and phenol. On the other hand, methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes having 6 and 9 methylene groups were found to be good for the selective para-chlorination of m-xylenol and m-cresol. Calculations using density functional theory on bis(methylthio)alkanes have suggested two different types of stable chlorinated intermediates depending on the number of methylene units as a spacer.

Computed tomography (CT) is commonly used to image intervertebral disc extrusion (IVDE) in dogs. The current gold standard for CT imaging is the use of multi-slice CT (MS CT) units. Smaller high-definition volumetric imaging (HDVI) mobile CT has been marketed for veterinary practice. This unit is described as an advanced flat panel. The goal of this manuscript was to evaluate the ability of the HDVI CT in detecting IVDE without the need for CT myelography, compared with the detection of acute disc extrusions with a MS CT without the need for MS CT myelogram. Retrospective blinded analyses of 219 dogs presented for thoraco-lumbar IVDE that had a HDVI CT (n = 123) or MS CT (n = 96) were performed at a single referral hospital. A total of 123 cases had HDVI CT scans with surgically confirmed IVDE. The IVDE was identified in 88/123 (72%) dogs on pre-contrast HDVI CT. The remaining 35/128 (28%) cases required a HDVI CT myelogram to identify the IVDE. Ninety-six cases had MS CT scans with surgically confirmed IVDE. The IVDE was identified in 78/96 (81%) dogs on the pre-contrast MS CT. The remaining 18/96 (19%) cases had a MS CT myelogram to identify the IVDE. Multi-slice CT detected IVDE significantly more than HDVI CT (p = 0.032). This study showed that the ability of HDVI CT for detecting IVDE is lower than that of MS CT. The HDVI CT system may be useful in smaller referral practices, with a lower case load where space is limited.

Thoraco-lumbar intervertebral disc extrusion is a common condition seen in veterinary practice. Although there are different surgical techniques described for decompression, most of these techniques are based on the surgeon’s preference or experience rather than clinical research. Our objective was to determine the clinical outcomes, using return to ambulation and micturition, as well as complication rates, in a large cohort of dogs by using a mini-hemilaminectomy for decompression of the thoraco-lumbar spinal cord with Hansen type I thoraco-lumbar intervertebral disc extrusions (IVDE). A retrospective study was performed on dogs presented for acute thoraco-lumbar IVDE undergoing surgical decompression. In total, 252 spinal decompression surgeries were performed. The recovery rates for patients graded with a modified Frankel score (MFS) of 5 to 0 were 100%, 99%, 100%, 96%, 86% and 64%, respectively. The mean days to micturition across all the MFS 5–0 were 1.5 (standard deviation [SD] ± 0.7), 1.8 (SD ± 1), 4.3 (SD ± 1.7), 6.4 (SD ± 2.2), 9.3 (SD 3) and 11.9 (SD ± 2.2), respectively. The mean days to ambulation across all the groups 5–0 were 2 (SD ± 0.7), 2.6 (SD ± 1), 7.6 (SD ± 4.4), 10.1 (SD ± 2.5), 16.1 (SD ± 2.9) and 19.3 (SD ± 2.6), respectively. Postoperative complications were seen in 32 of the surgeries, with a complication rate of 13%. Minor complications accounted for 38% of all complications, and major complications constituted 62% of all complications. In total, 15 dogs died or were euthanised as a direct result of thoraco-lumbar disc extrusion or the surgical procedure, with a mortality rate of 6% across all groups. A mini-hemilaminectomy provides similar clinical outcomes described in the literature for other methods of spinal cord decompressive surgery, and it also provides patients with similar short-term outcomes to other described decompressive surgical techniques in the dog, which have been described in the literature.

Known reagents that transfer three alkyl groups of a trialkylborane intramolecularly to a single carbon atom lack features to influence stereochemistry. We have investigated four reagents of type LiCCl2X, where X might be amenable to variation. All behaved differently. With X=OR (R=cyclohexyl, menthyl), the reagent decomposed, leading to only low yields of triple migration products. With X=S(O)Ph, a single migration occurred, followed by isomerisation to boron enolate-like species that hydrolysed to α-chloroalkyl phenyl sulfoxides or reacted with aldehydes to aldol-like products. With X=SO2Ph, the major product was the corresponding α,α-dichloroalkyl phenyl sulfone, apparently formed through a redox reaction. With X=S(O)(NMe)Ph, products of three intramolecular alkyl migrations were obtained with unhindered trialkylboranes. Attempts have been made to gain understanding of the sulfoxide process by investigating proportions of aldol-like products, using X-ray crystallography and ab initio calculations.

Introduction BRCA1 mutation carriers have a significant lifetime risk of breast cancer, with their primary risk-reduction option being bilateral mastectomy. Preclinical work from our laboratory demonstrated that in BRCA1-deficient breast cells, oestrogen and its metabolites are capable of driving DNA damage and subsequent genomic instability, which are well-defined early events in BRCA1-related cancers. Based on this, we hypothesise that a chemopreventive approach which reduces circulating oestrogen levels may reduce DNA damage and genomic instability, thereby providing an alternative to risk-reducing surgery. Methods and analysis 12 premenopausal women with pathogenic BRCA1 mutations and no previous risk-reducing surgery will be recruited from family history clinics. Participants will be allocated 1:1 to two arms. All will undergo baseline breast biopsies, blood and urine sampling, and quality of life questionnaires. Group A will receive goserelin 3.6 mg/28 days by subcutaneous injection, plus oral anastrozole 1 mg/day, for 12 weeks. Group B will receive oral tamoxifen 20 mg/day for 12 weeks. Following treatment, both groups will provide repeat biopsies, blood and urine samples, and questionnaires. Following a 1-month washout period, the groups will cross over, group A receiving tamoxifen and group B goserelin and anastrozole for a further 12 weeks. After treatment, biopsies, blood and urine samples, and questionnaires will be repeated. DNA damage will be assessed in core biopsies, while blood and urine samples will be used to measure oestrogen metabolite and DNA adduct levels. Ethics and dissemination This study has ethical approval from the Office for Research Ethics Committees Northern Ireland (16/NI/0055) and the Medicines and Healthcare products Regulatory Agency (MHRA) (reference: 32485/0032/001–0001). The investigational medicinal products used in this trial are licensed and in common use, with well-documented safety information. Dissemination of results will be via high-impact journals and relevant national/international conferences. A copy of the results will be offered to the participants and be made available to patient support groups. Trial registration number EudraCT: 2016-001087-11; Pre-results.

A review of Tom Mole's 'What the Victorians Made of the Romantics'.

Article about Nicholson and Ruskin and the environment for society periodical

Objective To evaluate changes in body position and effect of CO2 insufflation on the hepatobiliary and gastrointestinal systems using computed tomography (CT) to determine optimal laparoscopic approach. Study Design Experimental study. Animals Healthy intact female Beagles (n = 6) of similar age, weight, and body condition score. Methods Urinalysis, peripheral blood smear, and abdominal ultrasonography were performed to determine dog health. A series of pre insufflation (PrI) CT scans in ventrodorsal routine (VDR), ventrodorsal Trendelenburg (VDT), left lateral (LL), and right lateral (RL) recumbency were performed before and after abdominal insufflation (PoI) with CO2 (10–14 mm Hg). Pre-determined measurements were made on PrI and PoI scans and differences compared. Results Liver position was affected by body position and under gravitational influence moved to the dependent part of the abdominal cavity. The gallbladder was best exposed in LL. Stomach position was not significantly changed after insufflation. Different areas of small intestine were dependent on gravitational effects. The pancreas maintained a similar position after insufflation. Conclusions VDR was the ideal position for all laparoscopic procedures of the liver. The LL position could be used for surgery of the gallbladder but likely provides poor exposure to the rest of the liver. In approaching the stomach and intestines, the area of interest should be used to determine the best position.

This 'Thinking Space' piece considers the relationship between distant and close approaches to reading literary geographies. Specifically, it outlines recent developments in digital literary mapping, and suggests how the incorporation of these technologies in literary studies can advance new insights in the field.

Exploratory studies have demonstrated the benefits of implementing Geographic Information Systems (GIS) technology in literary and cultural-historical research. These studies have done much to affirm the power and flexibility of GIS technology as a resource for humanities scholarship. At the same time, however, these studies share a common limitation in that they tend to rely on the analysis of point-based cartographic representations. Such representations are suitable for modelling quantitative geographical phenomena, but they are inadequate for modelling qualitative human phenomena. This inadequacy constitutes a significant problem for researchers who aspire to analyse the geographical experiences and spatial relationships represented in works of literature, including works that contain accounts of travel. The present article proposes a solution to this problem by demonstrating how advanced spatial analyses within GIS such as Cost-Surface Analysis (CSA) and Least-Cost-Path Analysis (LCP) can be used to facilitate more nuanced interpretations of historical works of travel writing and topographical literature. Specifically, the article explains how GIS, CSA and LCP can be combined to build coherent spatial models of the journeys recorded in the works of three canonical eighteenth-century British travellers, each of whom composed influential accounts of their travels through the English Lake District: the poet Thomas Gray (1716–1771), the naturalist Thomas Pennant (1726–1798) and the agriculturist Arthur Young (1741–1820).