Simulating the Agostic Interaction in Electron-deficient (16-e) Group (VI) ML6 Complexes: [M(CO)5(C(Me)OMe)] (2+) (M = Cr, Mo, and W) as Models

A large number of theoretical studies have focused on understanding the molecular features of the agostic interaction in various kinds of molecular environments. However, there is a lack of electronic structure information about the agostic interaction in electron-deficient group (VI)ML6 organometallic complexes. In this simulation study, a unique case of an intramolecular stabilizing interaction has been discovered and evaluated. A geometric analysis revealed that beta-(C-H) and alpha-(C-C) can occupy the seventh and eighth coordination sites in the title Fischer carbene complexes as agostic interactions, which allows classifying the carbene as a η3 ligand in these cases. This theory was supported by the relative energies of the conformers and an NBO analysis. Both C2-C1 (σ) and C2-H1 (σ) were found to interact with the antibonding orbital of M-C6 (σ*), therefore these interactions are classified as σ→σ*. These two simultaneous interactions have significant impact on the carbene characteristics; the structure, the atomic charges, infrared stretching vibrations (C-H, C-C, and C-O), and the 1H and the 13C-NMR chemical shifts. From a fundamental organic-organometallic chemistry point of view, this is a new addition to the orbital interaction theory and to group (VI) chemistry.Keywords: DFT, agostic interaction, NBO analysis, NPA charges, IR, GIAO-NM

Machine learning models to detect anxiety and depression through social media : a scoping review

Despite improvement in detection rates, the prevalence of mental health disorders such as anxiety and depression are on the rise especially since the outbreak of the COVID-19 pandemic. Symptoms of mental health disorders have been noted and observed on social media forums such Facebook. We explored machine learning models used to detect anxiety and depression through social media. Six bibliographic databases were searched for conducting the review following PRISMA-ScR protocol. We included 54 of 2219 retrieved studies. Users suffering from anxiety or depression were identified in the reviewed studies by screening their online presence and their sharing of diagnosis by patterns in their language and online activity. Majority of the studies (70%, 38/54) were conducted at the peak of the COVID-19 pandemic (2019–2020). The studies made use of social media data from a variety of different platforms to develop predictive models for the detection of depression or anxiety. These included Twitter, Facebook, Instagram, Reddit, Sina Weibo, and a combination of different social sites posts. We report the most common Machine Learning models identified. Identification of those suffering from anxiety and depression disorders may be achieved using prediction models to detect user's language on social media and has the potential to complimenting traditional screening. Such analysis could also provide insights into the mental health of the public especially so when access to health professionals can be restricted due to lockdowns and temporary closure of services such as we saw during the peak of the COVID-19 pandemic

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Ocular Vascular Events following COVID-19 Vaccines: A Systematic Review

The main aim of this study is to investigate the current evidence regarding the association between COVID-19 vaccination and ocular vascular events. The protocol is registered on PROSPERO (CRD42022358133). On 18 August 2022, an electronic search was conducted through five databases. All original articles reporting individuals who were vaccinated with COVID-19 vaccines and developed ophthalmic vascular events were included. The methodological quality of the included studies was assessed using the NIH tool. A total of 49 studies with 130 ocular vascular cases were included. Venous occlusive events were the most common events (54.3%), which mostly occurred following the first dose (46.2%) and within the first five days following vaccination (46.2%). Vascular events occurred more with the Pfizer and AstraZeneca vaccines (81.6%), and mostly presented unilaterally (73.8%). The most frequently reported treatment was intravitreal anti-VEGF (n = 39, 30.4%). The majority of patients (90.1%) demonstrated either improvement (p = 0.321) or persistence (p = 0.414) in the final BCVA. Ophthalmic vascular events are serious vision-threatening side effects that have been associated with COVID-19 vaccination. Clinicians should be aware of the possible association between COVID-19 vaccines and ocular vascular events to provide early diagnosis and treatment

Oxime Amides as a Novel Zinc Binding Group in Histone Deacetylase Inhibitors: Synthesis, Biological Activity, and Computational Evaluation

Several oxime containing molecules, characterized by a SAEA-like structure, were explored to select a potentially new biasing binding element for the zinc in HDAC catalytic site. All compounds were evaluated for their in vitro inhibitory activity against the 11 human HDACs isoforms. After identification of a "hit" molecule, a programmed variation at the cap group and at the linker was carried out in order to increase HDAC inhibition and/or paralogue selectivity. Some of the new derivatives showed increased activity against a number of HDAC isoforms, even if their overall activity range is still far from the inhibition values reported for SAHA. Moreover, different from what was reported for their hydroxamic acid analogues the new alpha-oxime amide derivatives do not select between class I and class 11 HDACs; rather they target specific isoforms in each class. These somehow contradictory results were finally rationalized by a computational assisted SAR, which gave us the chance to understand how the oxime derivatives interact with the catalytic site and justify the observed activity profile

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Background: Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods: This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was coprioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low-middle-income countries. Results: In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of 'single-use' consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low-middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion: This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high- and low-middle-income countries