Development of Liquid Chromatography-Mass Spectrometry (LC-MS) Method for Quantification of Broccoli Sulforaphane

This is the final version. Available from Springer via the DOI in this record. The data that support the findings of this study are available from the corresponding author upon reasonable request.Sulforaphane (SFN) is an isothiocyanate and the product of the hydrolysis of glucoraphanin (GRA) by myrosinase. Broccoli is one of the rich sources of GRA and thus SFN. SFN possess a wide range of bioactivities and is considered an anti-cancer phytochemical. Most of the current common methods used to quantify SFN are based on high-pressure liquid chromatography (HPLC) with diode array detection (DAD) — also known as HPLC-DAD. Although this technique has shown encouraging results, the detection of SFN by DAD is relatively weak and affected by high interference of sample matrices. Therefore, the aim of this study was to develop a liquid chromatography-mass spectrometry (LC-MS) method in which SFN is identified by molecular mass to give more accurate results. The developed method demonstrated a highly reproducible retention time (7.204 ± 0.008 min), producing a sharp, symmetrical and well-defined sulforaphane peak in standard and test samples. The most dominant ion of sulforaphane in the pure and test samples was 178 m/z ([M + H]^+). In terms of linearity, the calibration curve had a coefficient of determination (R^2) of 0.9963. The limit of detection of this method is 1.3 ng/mL, and the limit of quantification is 3.9 ng/mL, indicating high sensitivity. The uniformity of peak shape and retention time in both pure and test samples were the same suggesting excellent selectivity. Overall, the developed method showed promising results in identifying and quantifying broccoli SFN.QUEX InstitutePepsiCo, In

Determination of glucosinolates and isothiocyanates in glucosinolate-rich vegetables and oilseeds using infrared spectroscopy: A systematic review.

This is the final version. Available from Taylor & Francis via the DOI in this recordCruciferous vegetables and oilseeds are rich in glucosinolates that can transform into isothiocyanates upon enzymic hydrolysis during post-harvest handling, food preparation and/or digestion. Vegetables contain glucosinolates that have beneficial bioactivities, while glucosinolates in oilseeds might have anti-nutritional properties. It is therefore important to monitor and assess glucosinolates and isothiocyanates content through the food value chain as well as for optimized crop production. Vibrational spectroscopy methods, such as infrared (IR) spectroscopy, are used as a nondestructive, rapid and low-cost alternative to the current and common costly, destructive, and time-consuming techniques. This systematic review discusses and evaluates the recent literature available on the use of IR spectroscopy to determine glucosinolates and isothiocyanates in vegetables and oilseeds. NIR spectroscopy was used to predict glucosinolates in broccoli, kale, rocket, cabbage, Brussels sprouts, brown mustard, rapeseed, pennycress, and a combination of Brassicaceae family seeds. Only one study reported the use of NIR spectroscopy to predict broccoli isothiocyanates. The major limitations of these studies were the absence of the critical evaluation of errors associated with the reference method used to develop the calibration models and the lack of interpretation of loadings or regression coefficients used to predict glucosinolates.QUEX Institut

Determination of glucosinolates in broccoli (Brassica oleracea var. italica) by combining mid‐infrared (MIR) spectroscopy with chemometrics

This is the final version. Available on open access from Wiley via the DOI in this recordData availability statement: The data that support the findings of this study are available from the corresponding author upon reasonable request.Glucosinolates (GSLs), compounds with potential chemo-preventative properties, can be affected by pre- and post-harvest processes. Therefore, monitoring their content is important for the food and agricultural industries. This study evaluates the application of mid-infrared (MIR) spectroscopy for the determination of GSLs in commercial broccoli (Brassica oleracea var. italica). Broccoli (n = 53) from different varieties were analysed using MIR spectroscopy and high-performance liquid chromatography to develop partial least squares models for six individual GLSs, total indolic glucosinolates and total GSLs. The coefficient of determination in cross-validation (R2cv) of 0.50–0.78 whereas residual predictive deviation (RPD) values of 1.35–2.19 for different GSLs. Cross-validation models developed using Tenderstem® broccoli yielded an of 0.41–0.91 and an RPD of 0.81–2.97. This study showed that MIR spectroscopy can be considered for the determination of some broccoli GSLs. Differences in the loadings between the models demonstrated that variations in broccoli composition can influence the cross-validation models for GSLs.PepsiCo, Inc.QUEX Institut

Qualitative analysis of broccoli (Brassica oleracea var. italica) glucosinolates: Investigating the use of mid-infrared spectroscopy combined with chemometrics

This is the final version. Available from Elsevier via the DOI in this record. Data Availability: No data was used for the research described in the article.Glucosinolates are phytochemicals with important health and nutritional benefits. This study reports the use of high-performance liquid chromatography (HPLC) and mid-infrared (MIR) spectroscopy to characterise and differentiate between broccoli varieties and systems of production (organic vs. non-organic) depending on their glucosinolate content and infrared fingerprint. Broccoli samples (n = 53) from seven varieties were analysed using MIR spectroscopy and HPLC. Differences in the MIR spectra of the individual broccoli varieties were observed in the carbohydrate fingerprint region (950–1100 cm-1) and between 1340 and 1615 cm-1 assigned to specific glucosinolates. Principal component analysis (PCA) of the MIR fingerprint spectra enabled the differentiation between samples with relatively high (200–500 mg/100 g DW) and low (< 200 mg/100 g DW) glucobrassicin content. Linear discriminant analysis (LDA) and PCA-LDA were used to classify broccoli varieties according to the system of production (organic vs. non-organic) and variety (common vs. Tenderstem® broccoli). The classification rates indicated that > 70 % of the samples were correctly classified as organic and non-organic, while > 90 % of the samples were correctly classified as common broccoli and Tenderstem®. This study demonstrates that MIR spectroscopy could be used as a potential tool to classify and monitor broccoli samples according to their variety and system of production.PepsiCoQUEX Institut

Characteristics of starch-based films plasticised by glycerol and by the ionic liquid 1-ethyl-3-methylimidazolium acetate: A comparative study

This paper reports the plasticisation effect of the ionic liquid, 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]), as compared with the traditionally used plasticiser, glycerol, on the characteristics of starch-based films. For minimising the additional effect of processing, a simple compression moulding process (which involves minimal shear) was used for preparation of starch-based films. The results show that [Emim][OAc] was favourable for plasticisation, i.e., disruption of starch granules (by scanning electron microscopy), and could result in a more amorphous structure in the starch-based materials (by X-ray diffraction and dynamic mechanical analysis). 13C CP/MAS and SPE/MAS NMR spectroscopy revealed that not only was the crystallinity reduced by [Emim][OAc], but also the amorphous starch present was plasticised to a more mobile form as indicated by the appearance of amorphous starch in the SPE/MAS spectrum. Mechanical results illustrate that, when either glycerol or [Emim][OAc] was used, a higher plasticiser content could contribute to higher flexibility. In spite of the accelerated thermal degradation of starch by [Emim][OAc] as shown by thermogravimetric analysis, the biodegradation study revealed the antimicrobial effect of [Emim][OAc] on the starch-based materials. Considering the high-amylose starch used here which is typically difficult to gelatinise in a traditional plasticiser (water and/or glycerol), [Emim][OAc] is demonstrated to be a promising plasticiser for starch to develop “green” flexible antimicrobial materials for novel applications

Visuo-tactile integration in autism: atypical temporal binding may underlie greater reliance on proprioceptive information

BackgroundEvidence indicates that social functioning deficits and sensory sensitivities in autism spectrum disorder (ASD) are related to atypical sensory integration. The exact mechanisms underlying these integration difficulties are unknown; however, two leading accounts are (1) an over-reliance on proprioception and (2) atypical visuo-tactile temporal binding. We directly tested these theories by selectively manipulating proprioceptive alignment and visuo-tactile synchrony to assess the extent that these impact upon body ownership.MethodsChildren with ASD and typically developing controls placed their hand into a multisensory illusion apparatus, which presented two, identical live video images of their own hand in the same plane as their actual hand. One virtual hand was aligned proprioceptively with the actual hand (the veridical hand), and the other was displaced to the left or right. While a brushstroke was applied to the participants’ actual (hidden) hand, they observed the two virtual images of their hand also being stroked and were asked to identify their real hand. During brushing, one of three different temporal delays was applied to either the displaced hand or the veridical hand. Thus, only one virtual hand had synchronous visuo-tactile inputs.ResultsResults showed that visuo-tactile synchrony overrides incongruent proprioceptive inputs in typically developing children but not in autistic children. Evidence for both temporally extended visuo-tactile binding and a greater reliance on proprioception are discussed.ConclusionsThis is the first study to provide definitive evidence for temporally extended visuo-tactile binding in ASD. This may result in reduced processing of amodal inputs (i.e. temporal synchrony) over modal-specific information (i.e. proprioception). This would likely lead to failures in appropriately binding information from related events, which would impact upon sensitivity to sensory stimuli, body representation and social processes such as empathy and imitation

Verbal thinking and inner speech use in autism spectrum disorder

The extent to which cognition is verbally mediated in neurotypical individuals is the subject of debate in cognitive neuropsychology, as well as philosophy and psychology. Studying “verbal thinking” in developmental/neuropsychological disorders provides a valuable opportunity to inform theory building, as well as clinical practice. In this paper, we provide a comprehensive, critical review of such studies among individuals with autism spectrum disorder (ASD). ASD involves severe social-communication deficits and limitations in cognitive/behavioural flexibility. The prevailing view in the field is that neither cognition nor behaviour is mediated verbally in ASD, and that this contributes to diagnostic features. However, our review suggests that, on the contrary, most studies to date actually find that among people with ASD cognitive task performance is either a) mediated verbally in a typical fashion, or b) not mediated verbally, but at no obvious cost to overall task performance. Overall though, these studies have methodological limitations and thus clear-cut conclusions are not possible at this stage. The aim of the review is to take stock of existing empirical findings, as well as to help develop the directions for future research that will resolve the many outstanding issues in this field

Evidence for a Grooming Claw in a North American Adapiform Primate: Implications for Anthropoid Origins

Among fossil primates, the Eocene adapiforms have been suggested as the closest relatives of living anthropoids (monkeys, apes, and humans). Central to this argument is the form of the second pedal digit. Extant strepsirrhines and tarsiers possess a grooming claw on this digit, while most anthropoids have a nail. While controversial, the possible presence of a nail in certain European adapiforms has been considered evidence for anthropoid affinities. Skeletons preserved well enough to test this idea have been lacking for North American adapiforms. Here, we document and quantitatively analyze, for the first time, a dentally associated skeleton of Notharctus tenebrosus from the early Eocene of Wyoming that preserves the complete bones of digit II in semi-articulation. Utilizing twelve shape variables, we compare the distal phalanges of Notharctus tenebrosus to those of extant primates that bear nails (n = 21), tegulae (n = 4), and grooming claws (n = 10), and those of non-primates that bear claws (n = 7). Quantitative analyses demonstrate that Notharctus tenebrosus possessed a grooming claw with a surprisingly well-developed apical tuft on its second pedal digit. The presence of a wide apical tuft on the pedal digit II of Notharctus tenebrosus may reflect intermediate morphology between a typical grooming claw and a nail, which is consistent with the recent hypothesis that loss of a grooming claw occurred in a clade containing adapiforms (e.g. Darwinius masillae) and anthropoids. However, a cladistic analysis including newly documented morphologies and thorough representation of characters acknowledged to have states constituting strepsirrhine, haplorhine, and anthropoid synapomorphies groups Notharctus tenebrosus and Darwinius masillae with extant strepsirrhines rather than haplorhines suggesting that the form of pedal digit II reflects substantial homoplasy during the course of early primate evolution

Cheek Tooth Morphology and Ancient Mitochondrial DNA of Late Pleistocene Horses from the Western Interior of North America: Implications for the Taxonomy of North American Late Pleistocene Equus

Horses were a dominant component of North American Pleistocene land mammal communities and their remains are well represented in the fossil record. Despite the abundant material available for study, there is still considerable disagreement over the number of species of Equus that inhabited the different regions of the continent and on their taxonomic nomenclature. In this study, we investigated cheek tooth morphology and ancient mtDNA of late Pleistocene Equus specimens from the Western Interior of North America, with the objective of clarifying the species that lived in this region prior to the end-Pleistocene extinction. Based on the morphological and molecular data analyzed, a caballine (Equus ferus) and a non-caballine (E. conversidens) species were identified from different localities across most of the Western Interior. A second non-caballine species (E. cedralensis) was recognized from southern localities based exclusively on the morphological analyses of the cheek teeth. Notably the separation into caballine and non-caballine species was observed in the Bayesian phylogenetic analysis of ancient mtDNA as well as in the geometric morphometric analyses of the upper and lower premolars. Teeth morphologically identified as E. conversidens that yielded ancient mtDNA fall within the New World stilt-legged clade recognized in previous studies and this is the name we apply to this group. Geographic variation in morphology in the caballine species is indicated by statistically different occlusal enamel patterns in the specimens from Bluefish Caves, Yukon Territory, relative to the specimens from the other geographic regions. Whether this represents ecomorphological variation and/or a certain degree of geographic and genetic isolation of these Arctic populations requires further study