Isolation and extraction of lucidin primeveroside from Rubia tinctorum L. and crystal structure elucidation

Madder (Rubia tinctorum L.) has been used as a dye for over 2000 years with alizarin and purpurin the major natural dyes analysed from extractions undertaken. The use of ethanol as the solvent in the extraction process produced an extract that yielded four anthraquinone compounds lucidin primeveroside, ruberythric acid, alizarin and lucidin-ω-ethyl ether. Gravitational separation of the extract was used to record the first crystal structure of lucidin primeveroside, which is also the first ever known crystal structure of a glycoside containing anthraquinone moiety. The crystal structure along with 1H and 13C NMR helped elucidate and confirm the structure of this overlooked natural dye which has been shown to be a major compound in R. tinctorum L

Chest radiographs and machine learning - Past, present and future.

Despite its simple acquisition technique, the chest X-ray remains the most common first-line imaging tool for chest assessment globally. Recent evidence for image analysis using modern machine learning points to possible improvements in both the efficiency and the accuracy of chest X-ray interpretation. While promising, these machine learning algorithms have not provided comprehensive assessment of findings in an image and do not account for clinical history or other relevant clinical information. However, the rapid evolution in technology and evidence base for its use suggests that the next generation of comprehensive, well-tested machine learning algorithms will be a revolution akin to early advances in X-ray technology. Current use cases, strengths, limitations and applications of chest X-ray machine learning systems are discussed

Enhancing the potential exploitation of food waste: Extraction, purification, and characterization of renewable specialty chemicals from blackcurrants (Ribes nigrum L.)

Natural colorants were extracted from renewable botanical sources, specifically waste epicarp from the blackcurrant fruit pressing industry. A process was developed which used acidified water extraction followed by a solid-phase extraction (SPE) purification stage which allowed the production of an anthocyanin-rich extract in good yields (ca. 2% w/w based on dry weight of raw material). The components in the extracts were extensively characterized by HPLC, mass spectrometry, IR, NMR and UV-Vis spectroscopy. HPLC confirmed presence of four anthocyanins: delphinidin-3-O-rutinoside (45%), cyanidin-3-O-rutinoside (31%) and the corresponding glucosides at 16% and 8%, respectively. On sequential liquid-liquid aqueous-organic partitioning of the post-SPE sample, monomeric anthocyanins (54.7%) and polymeric anthocyanins (18%) were found in the aqueous layer with 3-O-rutinosides of myricetin (3.1%) and quercetin (3.2%), whilst isopropylacetate achieved selective extraction of caffeic acid (3%), p-coumaric acid (5%), and myricetin (2.5%) and quercetin (3.2%) aglycons. 3-O-Glucosides of myricetin (3.1%) and quercetin (2%), along with nigrumin-p-coumarate (1%) and nigrumin ferulate (0.5%) were selectively extracted from the remaining aqueous fraction using ethylacetate. This allowed for near total quantification of the blackcurrant extract composition

Assessment of the effect of a comprehensive chest radiograph deep learning model on radiologist reports and patient outcomes: a real-world observational study.

OBJECTIVES: Artificial intelligence (AI) algorithms have been developed to detect imaging features on chest X-ray (CXR) with a comprehensive AI model capable of detecting 124 CXR findings being recently developed. The aim of this study was to evaluate the real-world usefulness of the model as a diagnostic assistance device for radiologists. DESIGN: This prospective real-world multicentre study involved a group of radiologists using the model in their daily reporting workflow to report consecutive CXRs and recording their feedback on level of agreement with the model findings and whether this significantly affected their reporting. SETTING: The study took place at radiology clinics and hospitals within a large radiology network in Australia between November and December 2020. PARTICIPANTS: Eleven consultant diagnostic radiologists of varying levels of experience participated in this study. PRIMARY AND SECONDARY OUTCOME MEASURES: Proportion of CXR cases where use of the AI model led to significant material changes to the radiologist report, to patient management, or to imaging recommendations. Additionally, level of agreement between radiologists and the model findings, and radiologist attitudes towards the model were assessed. RESULTS: Of 2972 cases reviewed with the model, 92 cases (3.1%) had significant report changes, 43 cases (1.4%) had changed patient management and 29 cases (1.0%) had further imaging recommendations. In terms of agreement with the model, 2569 cases showed complete agreement (86.5%). 390 (13%) cases had one or more findings rejected by the radiologist. There were 16 findings across 13 cases (0.5%) deemed to be missed by the model. Nine out of 10 radiologists felt their accuracy was improved with the model and were more positive towards AI poststudy. CONCLUSIONS: Use of an AI model in a real-world reporting environment significantly improved radiologist reporting and showed good agreement with radiologists, highlighting the potential for AI diagnostic support to improve clinical practice

Atmospheric CO2 and d13C-CO2 reconstruction of the little ice age from antarctic ice cores

The decrease of atmospheric CO2 concentration recorded in Antarctic ice around 1600 AD is one of the most significant atmospheric changes to have occurred during the last millennia, before the onset of the industrial period.Together with the temperature decrease, the CO2 drop has been used to derive the sensitivity of carbon stores to climate. However, the cause of it is still under debate because models are not yet able to reproduce either its magnitude, or its timing. Here we present new measurements of the CO2 concentration decrease recorded in an ice core from a medium accumulation rate site in Antarctica (DML). We show that the new record is compatible(differences <2 ppm) with the CO2 record from the high accumulation rate DSS site on Law Dome (East Antarctica), when the different age distributions are taken into account. We have also measured the d13C-CO2 change in DML ice, filling a gap around 1600 AD in the DSS d13C record. We use a double deconvolution of the CO2 and d13C records together to provide quantitative evidence that the CO2 decrease was caused by a change in the net flux to the terrestrial biosphere. Finally, we provide a new interpretation of a published record showing increasing atmospheric carbonyl sulphide during the CO2 decrease, suggesting that cooler LIA climate affected terrestrial biospheric fluxes. Altogether our findings support the hypothesis that reduced soil heterotrophic respiration is likely to have given the most significant contribution to the LIA CO2 decrease implying a positive CO2-climate feedback. © 2015, Authors

Guanidine-Catalyzed Reductive Amination of Carbon Dioxide with Silanes: Switching between Pathways and Suppressing Catalyst Deactivation

A mechanistic investigation into the guanidine-catalyzed reductive amination of CO₂, using a combination of ¹H, ²⁹Si NMR, FT-IR, MS, and GC profiling, is reported. Inexpensive and readily available N,N,N′,N′-tetramethylguanidine (TMG) was found to be an equally effective catalyst compared to more elaborate cyclic guanidines. Different catalytic pathways to formamide 2, aminal 4, and N-methylamine 3 were identified. A pathway to formamide product 2 dominates at 23 °C. Increasing the reaction temperature to 60 °C enables a competitive, higher-energy pathway to 4 and 3, which requires direct reduction of CO₂ with PhSiH₃ to formoxysilane E. Reduction of aminal 4, in the presence of CO₂ and the catalyst, led to formation of a 1:1 ratio of 2 and 3. The catalyst itself can be formylated under the reaction conditions, resulting in its deactivation. Thus, alkylated TMGs were found to be more stable and more active catalysts than TMG, leading to a successful organocatalyzed reductive functionalization of CO₂ with silane at 0.1 mol % catalyst loading (TON = 805 and TOF = 33.5 h‾¹)

Selective enzymatic lipophilization of anthocyanin glucosides from blackcurrant (Ribes nigrum L.) skin extract and characterization of esterified anthocyanins

Anthocyanins (ANC) are hydrophilic and water-soluble polyphenolic plant pigments. The current barriers to successful application of ANC in food, cosmetic and pharmaceutical industries are predominantly related to performance, stability, formulation properties, and color. Enzymatic acylation of ANC could increase their stability without compromising bioactivity and chromatic features. Lipophilization of ANC-rich blackcurrant skin extract with Candida antarctica lipase B and octanoic acid was selective to cyanidin and delphinidin glucosides, but not the corresponding rutinosides. The reaction was chemo- and regioselective for acylation at the primary alcohol of the glucose moieties, greatly facilitating separation of the different glycoside derivatives

Defining eye-fixation sequences across individuals and tasks: the Binocular-Individual Threshold (BIT) algorithm

We propose a new fully automated velocity-based algorithm to identify fixations from eye-movement records of both eyes, with individual-specific thresholds. The algorithm is based on robust minimum determinant covariance estimators (MDC) and control chart procedures, and is conceptually simple and computationally attractive. To determine fixations, it uses velocity thresholds based on the natural within-fixation variability of both eyes. It improves over existing approaches by automatically identifying fixation thresholds that are specific to (a) both eyes, (b) x- and y- directions, (c) tasks, and (d) individuals. We applied the proposed Binocular-Individual Threshold (BIT) algorithm to two large datasets collected on eye-trackers with different sampling frequencies, and compute descriptive statistics of fixations for larger samples of individuals across a variety of tasks, including reading, scene viewing, and search on supermarket shelves. Our analysis shows that there are considerable differences in the characteristics of fixations not only between these tasks, but also between individuals

A comparison of hospital readmission rates between two general physicians with different outpatient review practices

BACKGROUND: There has been a relentless increase in emergency medical admissions in the UK over recent years. Many of these patients suffer with chronic conditions requiring continuing medical attention. We wished to determine whether conventional outpatient clinic follow up after discharge has any impact on the rate of readmission to hospital. METHODS: Two consultant general physicians with the same patient case-mix but markedly different outpatient follow-up practice were chosen. Of 1203 patients discharged, one consultant saw twice as many patients in the follow-up clinic than the other (Dr A 9.8% v Dr B 19.6%). The readmission rate in the twelve months following discharge was compared in a retrospective analysis of hospital activity data. Due to the specialisation of the admitting system, patients mainly had cardiovascular or cerebrovascular disease or had taken an overdose. Few had respiratory or infectious diseases. Outpatient follow-up was focussed on patients with cardiac disease. RESULTS: Risk of readmission increased significantly with age and length of stay of the original episode and was less for digestive system and musculo-skeletal disorders. 28.7% of patients discharged by Dr A and 31.5 % of those discharged by Dr B were readmitted at least once. Relative readmission risk was not significantly different between the consultants and there was no difference in the length of stay of readmissions. CONCLUSIONS: Increasing the proportion of patients with this age- and case-mix who are followed up in a hospital general medical outpatient clinic is unlikely to reduce the demand for acute hospital beds