Modelling on a Biomimetic [Cu-O-Cu]2+-mediated Methane-to-Methanol Conversion Unveils the Site for Methane Activation.

The Cu-O-Cu core exhibits methane-to-methanol conversion, mirroring the reactivity of the copper-containing enzyme pMMO. Herein, we computationally examined the reactivity of a biomimetic Cu-O-Cu core towards methane-to-methanol conversion. The oxygen atom of the Cu-O-Cu core abstracts hydrogen present in the C-H bond of methane. The spin density at the bridging oxygen helps to abstract hydrogen from the C-H bond. We modulated the spin density of the bridging oxygen by substituting only a single copper atom of the Cu-O-Cu core by metals (M) such as Fe, Co, and Ag. These substitutions result in bimetallic [Cu-O-M]2+ models. We observed that the energy barriers for the C-H activation step and the subsequent rebound step vary with the metal M. [Cu-O-Ag]2+ exhibits the highest reactivity for M2M conversion, while [Cu-O-Fe]2+ displays the lowest reactivity. To understand the different reactivity of these models towards M2M conversion, we employed distortion-interaction analysis, orbital analysis, spin density analysis, and quantum theory of atoms in molecules analysis. Orbital analysis reveals that all four adducts follow a hydrogen atom transfer mechanism for C-H activation. Further, spin density analysis reveals that a higher spin density on the bridging oxygen leads to a lower C-H activation barrier.

Unidentical Twins: Geometrically Similar but Chemically Distinct Metal-free Sites in Boron Oxide for Methane Oxidation to HCHO, CO and CO2.

Metal-free boron-based catalysts such as boron oxide (B2O3) and boron nitride (h-BN) are promising catalysts for the methane oxidation to HCHO and CO. The B2O3 catalyst contains various probable boron sites (B1 to B6), which may be responsible for methane oxidation. In this work, we utilized density functional theory to compare two relevant geometrically identical boron sites (B2 and B4) for their reactivities. The two sites are explored in-detail for the conversion of methane to formaldehyde (M2F), carbon monoxide and carbon dioxide. The B4 site activates the methane C-H bond easily as compared to the B2 site. In M2F conversion, the rate-determining step for the B2 site is the co-activation of dioxygen and methane, whereas over the B4 site, formaldehyde formation is the rate-determining step. The computationally-determined RDS for the B4 site coincides well with the reported experiments. It is further revealed that this site also prefers the formation of CO over CO2, which is in-line with the experiments in literature. It is also shown through orbital analysis that methanol formation does not occur during methane oxidation. We employed descriptors such as condensed Fukui functions and global electrophilicity index to chemically distinct these twin sites.

DFT Struggles to Predict the Energy Landscape for Iron Pyridine Diimine-Catalyzed [2 + 2] Cycloaddition of Alkenes: Insights into the Problem and Alternative Solutions.

In recent years, noninnocent pyridine diimine (PDI) complexes featuring first-row transition metals have emerged as prominent catalysts, demonstrating efficacy in a diverse range of vital organometallic transformations. However, the inherent complexity of the fundamental reactivity paradigm in these systems arises from the presence of a noninnocent ligand and the multispin feasibility of 3d metals. While density functional theory (DFT) has been widely used to unravel mechanistic insights, its limitations as a single-reference method can potentially misrepresent spin-state energetics, compromising our understanding of these intricate systems. In this study, we employ extensive high-level ab initio state averaged-complete active space self-consistent field/N-electron valence state perturbation theory (SA-CASSCF/NEVPT2) calculations in combination with DFT to investigate an iron-PDI-catalyzed [2 + 2] cycloaddition reaction of alkenes. The transformation proceeds through two major steps: oxidative cyclization and reductive elimination. Contrary to the predictions of DFT calculations, which suggest two-state reactivity in the reaction and identify reductive elimination as the turnover-limiting step, SA-CASSCF/NEVPT2-corrected results unequivocally establish a single-state reactivity scenario with oxidative cyclization as the turnover-limiting step. SA-CASSCF/NEVPT2-based insights into electronic ground states and electron distribution elucidate the intriguing interactions between the PDI ligand and the iron center, revealing the highly multiconfigurational nature of these species and providing a precise depiction of metal-ligand cooperativity throughout the transformation. A comparative assessment of several widely recognized DFT functionals against SA-CASSCF/NEVPT2-corrected data indicates that single-point energy calculations using the modern density functional MN15 on TPSSh geometries offer the most reliable density functional methodology, in scenarios where SA-CASSCF/NEVPT2 computational cost is a consideration.

Nanophytosomal Gel of Heydotis corymbosa (L.) Extract against Psoriasis: Characterisation, In Vitro and In Vivo Biological Activity.

The current study was conducted to examine the possible advantages of Heydotis corymbosa (L.) Lam. extract nanogel as a perspective for enhanced permeation and extended skin deposition in psoriasis-like dermatitis. Optimised nanophytosomes (NPs) were embedded in a pluronic gel base to obtain nanogel and tested ex vivo (skin penetration and dermatokinetics) and in vivo. The optimised NPs had a spherical form and entrapment efficiency of 73.05 ± 1.45% with a nanosized and zeta potential of 86.11 nm and -10.40 mV, respectively. Structural evaluations confirmed encapsulation of the drug in the NPs. Topical administration of prepared nanogel to a rat model of psoriasis-like dermatitis revealed its specific in vivo anti-psoriatic efficacy in terms of drug activity compared to the control and other formulations. Nanogel had improved skin integrity and downregulation of inflammatory cytokines. These findings suggest that developed phytoconstituent-based nanogel has the potential to alleviate psoriasis-like dermatitis with better skin retention and effectiveness.

Mapping the Catalytic-Space for the Reactivity of Metal-free Boron Nitride with O2 for H2O-Mediated Conversion of Methane to HCHO and CO.

Transition-metal based catalysts have been widely employed to catalyze partial oxidation of light alkanes. Recently, metal-free hexagonal-boron nitride (h-BN) has emerged as a promising catalyst for the oxidation of CH4 to HCHO and CO; however, the intricate catalytic surface of h-BN at molecular and electronic levels remains inadequately understood. Key questions include how electron-deficient boron atoms in h-BN reduce O2, and whether the partial oxidation of methane over h-BN exhibits similarities to traditional transition-metal catalysts. In our study, we computationally-mapped in-detail the surface catalytic-space of h-BN for methane oxidation. We considered different structures of h-BN and show that these structures contain numerous sites for O2 binding and therefore various routes for methane oxidation are possible. The activation barriers for methane oxidation via various paths varies from ~83 to ~123 kcal mol-1. To comprehend the differences in activation barriers, we employed geometrical, orbital and distortion/interaction analysis (DIA). Orbital analysis reveals that methane activation over h-BN in presence of dioxygen follows a standard hydrogen atom transfer mechanism. It is also shown that water plays an intriguing role in reducing the barrier for HCHO and CO formation by acting as a bridge.

Orbital Analysis Captures the Existence of a Mixed-Valent CuIII -O-CuII Active-Site and its Role in Water-Assisted Aliphatic Hydroxylation.

The Cu-O-Cu core has been proposed as a potential site for methane oxidation in particulate methane monooxygenase. In this work, we used density functional theory (DFT) to design a mixed-valent CuIII -O-CuII species from an experimentally known peroxo-dicopper complex supported by N-donor ligands containing phenolic groups. We found that the transfer of two-protons and two-electrons from phenolic groups to peroxo-dicopper core takes place, which results to the formation of a bis-µ-hydroxo-dicopper core. The bis-µ-hydroxo-dicopper core converts to a mixed-valent CuIII -O-CuII core with the removal of a water molecule. The orbital and spin density analyses unravel the mixed-valent nature of CuIII -O-CuII . We further investigated the reactivity of this mixed-valent core for aliphatic C-H hydroxylation. Our study unveiled that mixed-valent CuIII -O-CuII core follows a hydrogen atom transfer mechanism for C-H activation. An in-situ generated water molecule plays an important role in C-H hydroxylation by acting as a proton transfer bridge between carbon and oxygen. Furthermore, to assess the relevance of a mixed-valent CuIII -O-CuII core, we investigated aliphatic C-H activation by a symmetrical CuII -O-CuII core. DFT results show that the mixed-valent CuIII -O-CuII core is more reactive toward the C-H bond than the symmetrical CuII -O-CuII core.

Crystal structure of a phenoxyl radical complex relevant to the metal site of the galactose oxidase enzyme: A facile one-pot synthesis, evidence for hydrogen atom transfer and DNA cleavage via self-activation.

Copper complexes [Cu(L1H)ClO4] (1) and [Cu(L2)NO3] (2), which are relevant to the metal site of the galactose oxidase enzyme, were synthesized and characterized by different spectroscopic methods. L1H2 and L2H2 [where L1H2 stands for 2,2'-((1E,1'E)(2,2'-(pyridine-2,6-diyl)bis(2-phenylhydrazin-2-yl-1-ylidene))bis(methanylylidene))diphenol and L2H2 stands for 6,6'-((1E,1'E)-(2,2'-(pyridine-2,6-diyl)bis(2-phenylhydrazin-2-yl-1-ylidene))bis(methanylylidene))bis(2,4-di-tert-butylphenol), H stands for dissociable proton] are pentadentate ligands. These ligands provide pyridyl N, two imine N, and two non-innocent phenoxyl and phenolato O donors, forming complex 1 as a non-radical complex, while complex 2 is a phenoxyl radical complex. The molecular structures of complexes 1 and 2 were authenticated by X-ray crystallography. Benzyl alcohol oxidation was investigated, and the conversion of 9,10-dihydroanthracene to anthracene was examined to scrutinize the H-atom abstraction reaction. Nuclease activity with complexes 1 and 2 was investigated by self-activated plasmid DNA (pBR322) cleavage. Non-innocent properties of the ligand-containing phenolato function were investigated by DFT calculations.

Use of i-Gel Supraglottic Airway in a Simulated Cardiac Arrest Resuscitation During Boat Rescue Transport by Los Angeles County Fire Lifeguard Division: A Proof-of-Concept Study.

OBJECTIVE: The Los Angeles County Fire Department Lifeguard Division responds to water rescues and medical and dive emergencies across 72 miles of Southern California coastline and Catalina Island. Limited advanced life support resources make cardiac arrest resuscitations logistically challenging during transport to shore or the hyperbaric chamber. This proof-of-concept study looked to determine if an i-Gel (Intersurgical Complete Respiratory Systems, Wokingham, Berkshire, UK) supraglottic airway device would either become dislodged or compromise ventilations during prolonged resuscitation at high speeds over open water with an ongoing automatic chest compression device (ACCD). METHODS: A simulated resuscitation was performed on the Los Angeles County Lifeguard rescue boat while underway at speeds up to 25 knots. A LUCAS ACCD (Jolife AB, Ideon Science Park, Lund, Sweden) and a size 3 i-Gel were used. The volume of ventilations and depth of compressions were continuously monitored using the AmbuMan Advanced manikin (Ambu, Ballerup, Denmark). RESULTS: The i-Gel supraglottic airway device delivered appropriate ventilations measuring between 300 and 400 mL/breath when delivered on the upstroke of compression. The i-Gel did not dislodge during transport. CONCLUSION: The i-Gel supraglottic airway device appears to provide adequate ventilations without dislodgment during ongoing compressions with an ACCD during high-speed water transport.

Patient-reported outcomes measurement information system instruments in knee arthroplasty patients: a systematic review of the literature.

BACKGROUND: The purpose of this study is to provide a systematic review of the literature pertaining to Patient-Reported Outcome Measurement Information System (PROMIS) validation and utilization as an outcomes metric in total knee arthroplasty (TKA) patients. This is the first systematic review on PROMIS use in total knee arthroplasty patients. METHODS: A systematic search of the Pubmed/MEDLINE and Embase databases was performed according to the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines. Study characteristics, patient demographics, psychometric properties (Pearson and Spearman correlation) with legacy patient-reported outcome measurement (PROM) instruments, floor and ceiling effects, responsiveness, and minimum clinically important difference (MCID) and PROMIS outcomes were recorded and analyzed. RESULTS: Fifteen studies investigating PROMIS in 11,140 patients were included. The weighted-average Pearson correlation coefficient comparing PROMIS domains with legacy patient-reported outcome measurements in total knee arthroplasty patients was 0.62 [standard error (SE) = 0.06] and the weighted-average Spearman correlation comparing PROMIS domains with legacy patient-reported outcome measurements in total knee arthroplasty patients was 0.59 (SE = 0.06), demonstrating moderate-to-strong correlation and validity. There were no differences in weighted average floor [0.03% (SE = 3.1) versus 0% (SE = 0.1) versus 0.01% (SE = 1.1); p = 0.25] or ceiling effects [0.01% (SE = 0.7) versus 0.02% (SE = 1.4) versus 0.04% (SE = 3.5); p = 0.36] between PROMIS and legacy instruments. The weighted average for percentage of patients achieving MCID was 59.1% for global physical health (GPH), 26.0% for global mental health (GMH), 52.7% for physical function (PF), 67.2% for pain interference (PI), and 37.2% for depression. CONCLUSION: Notably, PROMIS global physical health, physical function, and pain interference were found to be significantly responsive, with PROMIS pain interference most effectively capturing clinical improvement as evidenced by the achievement of MCID.

Determinants of Unsupervised Medical Termination of Pregnancy Pill Usage Among Women: A Cross-Sectional Study From North India.

Background Medical termination of pregnancy (MTP) pills, primarily comprising mifepristone and misoprostol, have proven highly effective and safe under medical supervision. However, unsupervised MTP pill use is on the rise, posing serious health risks. Unsafe abortions remain a global public health concern, with a high incidence in developing countries like India. Methods We conducted a cross-sectional study at a tertiary healthcare center in India from February to April 2023. We enrolled 150 women with a history of unsupervised MTP pill use. Data were collected using structured questionnaires, including demographic information, awareness, sources of information, reasons for self-medication, and knowledge of complications. Results The majority of participants (50%) were aged 25-29 years. Low-income women (<3000pc) constituted 46.66% of the sample. Husbands played a significant role in advocating MTP pill use (57.33%). Ninety percent of pills were obtained directly from pharmacies. Shockingly, 97.3% of women were unaware of MTP pill complications, and 84% did not follow the recommended regimen. Significant associations were found between income, religion, education, age, parity, and reasons for self-medication, as well as recommendations for MTP pill use. Conclusion Our study revealed a diverse demographic of women seeking unsupervised MTP pill intake. Low-income women were disproportionately affected, emphasizing the need for improved healthcare access and education. Husbands played a crucial role in advocating MTP pill use, highlighting the importance of including men in reproductive health discussions. Lack of awareness and non-adherence to recommended regimens posed substantial risks. To combat unsafe abortions, a multifaceted approach is needed. Reproductive health education, regulatory measures, improved healthcare accessibility, and tailored interventions are essential.

Perceptions and factors associated with COVID Appropriate Behavior (CAB) obedience among general public in India: A mixed methods research.

BACKGROUND: The purpose of the study was to analyze the public perception toward COVID Appropriate Behavior (CAB) obedience and to identify the factors associated with declining CAB. MATERIALS AND METHODS: It is a mixed methods study conducted from November 2021 to September 2022 in Pune city, India. A set of 15-CAB guidelines published by the Ministry of Health and Family Welfare, Government of India (GoI), were used as a base document to design the instruments of qualitative and quantitative study. Using a one-sample Kolmogorov-Smirnov test, CAB scores were tested for normality and distribution. Comparisons of various parameters were done using z test for proportion and paired t-test (statistical significance level was 0.05). Thematic content analysis was conducted for qualitative data analysis and verbatims are reported where applicable. RESULTS: The main motivation for people to get vaccinated was family and personal safety and a higher proportion of people felt safer post-vaccination which was linked to a reduced likelihood of CAB obedience. Qualitative results showed that people's lack of empathy and concern for others leads to undesirable personal behaviors such as spitting in public places, not wearing masks, etc., The need for socialization is high but discomfort with the use of masks/face shields and habituation with the disease were prominent causes of CAB disobedience. CONCLUSION: We conclude that reduced fear and gradual habituation have led to reduced CAB obedience. There is a need to reinforce empathy and concern for others to improve adherence to CAB like maintaining social distancing and wearing masks in public places for personal and social safety from the disease.

Venous thromboembolism following surgical management of proximal humerus fractures: a systematic review.

Background: Currently, there is limited information on the incidence of venous thromboembolism (VTE), including deep vein thrombosis (DVT) and pulmonary embolism (PE) after surgical treatment of proximal humerus fractures (PHFs). Therefore, the purpose of this systematic review is to evaluate the incidence of VTE, DVT, and PE following surgery for PHFs. Methods: A comprehensive search of several databases was performed from inception to May 27, 2022. Studies were screened and evaluated by 2 reviewers independently utilizing the Preferred Reporting Items for Systematic Reviews and Meta-Analysis (PRISMA) guidelines. Only original, English studies that evaluated the incidences of VTE following surgical management of PHFs were included. Surgical procedures consisted of shoulder arthroplasty (SA) including both hemiarthroplasty (Hemi) and reverse shoulder arthroplasty (RSA) in addition to open reduction and internal fixation (ORIF). A pooled incidence for postoperative DVT, PE, and overall VTE was reported. Results: Twelve studies met the inclusion and exclusion criteria, encompassing a total of 18,238 patients. The overall DVT, PE, and VTE rates were 0.14%, 0.59%, and 0.7%, respectively. VTE was more frequently reported after SA than ORIF, (1.27% vs. 0.53%, respectively). Among SA patients, a higher rate of DVT was seen with RSA (1.2%) with the lowest DVT rate was observed for ORIF with 0.03%. Conclusions: Symptomatic VTEs following surgical treatment of PHFs, are rare, yet still relevant as a worrisome postoperative complication. Among the various procedures, VTE was the most frequently reported after SA when compared to ORIF, with RSA having the highest VTE rate.

Current clinical applications of artificial intelligence in shoulder surgery: what the busy shoulder surgeon needs to know and what's coming next.

Background: Artificial intelligence (AI) is a continuously expanding field with the potential to transform a variety of industries-including health care-by providing automation, efficiency, precision, accuracy, and decision-making support for simple and complex tasks. Basic knowledge of the key features as well as limitations of AI is paramount to understand current developments in this field and to successfully apply them to shoulder surgery. The purpose of the present review is to provide an overview of AI within orthopedics and shoulder surgery exploring current and forthcoming AI applications. Methods: PubMed and Scopus databases were searched to provide a narrative review of the most relevant literature on AI applications in shoulder surgery. Results: Despite the enormous clinical and research potential of AI, orthopedic surgery has been a relatively late adopter of AI technologies. Image evaluation, surgical planning, aiding decision-making, and facilitating patient evaluations over time are some of the current areas of development with enormous opportunities to improve surgical practice, research, and education. Furthermore, the advancement of AI-driven strategies has the potential to create a more efficient medical system that may reduce the overall cost of delivering and implementing quality health care for patients with shoulder pathology. Conclusion: AI is an expanding field with the potential for broad clinical and research applications in orthopedic surgery. Many challenges still need to be addressed to fully leverage the potential of AI to clinical practice and research such as privacy issues, data ownership, and external validation of the proposed models.

Impact of Obesity on Anterior Cervical Discectomy and Fusion (ACDF): Postoperative Morbidity and Mortality.

AIM: To investigate the impact of obesity on postoperative morbidity and mortality in patients who underwent anterior cervical discectomy and fusion (ACDF). MATERIAL AND METHODS: The American College of Surgeons' National Surgical Quality Improvement Project (NSQIP) files from 2006 to 2019 were queried for all patients who underwent an ACDF. Fisher exact tests were used in analyzing univariate differences in preoperative comorbidities and postoperative morbidity and mortality between patients with and without obesity (BMI ?30 kg/ m < sup > 2 < /sup > ). Results with a p value < 0.05 were considered statistically significant. Multivariable logistic regression models were used in determining the independent impact of obesity on ACDF postoperative morbidity and mortality. A p value < 0.017 was required for multivariate statistical significance. RESULTS: There were 96,882 patients who underwent an ACDF from 2006 to 2019 found. 53.77% had non-obese BMI. Patients had statistically significant differences in most perioperative comorbidities and postoperative outcomes on univariate analysis. On multivariate analysis, patients with obesity has decreased adjusted odds of wound infections (aOR=0.7208, CI 0.574-0.9075, p=0.0053), pulmonary events (aOR=0.7939, CI 0.6903-0.9129, p=0.0012), sepsis (aOR=0.5670, CI 0.4359-0.7374, p=2.32E-05), transfusion requirements (aOR=0.5396, CI 0.4498-0.6473, p=3.04E-11), return to operating room (aOR=0.7537, CI 0.6727-0.8447, p=1.17E-06), and length of stay > 10 days (aOR=0.7061, CI 0.6438-0.7744, p=1.49E-13). CONCLUSION: Obesity is a protective factor toward ACDF postoperative complications. Obesity as a marker of patient selection criteria for ACDF procedures should not be used by spine surgeons.

2-Hydroxypyridine-based Ligands as Promoter in Ruthenium(II) Catalyzed C-H Bond Activation/Arylation Reactions.

A class of 2-hydroxypyridine based ligands are explored to achieve enhanced catalytic activity for ortho-C-H bond activation/arylation reaction over [(η6 -p-cymene)RuCl2 ]2 catalyst in water. Extensive studies using a series of substituted 2-hydroxypyridine based ligands (L1-L6) inferred that 5-trifluoromethyl-2-hydroxypyridine (L6) exhibited favorable effects to enhance the catalytic activity of Ru(II) catalyst for ortho C-H bond arylation of 2-phenylpyridine by 8 folds compared to those performed without ligands. The (η6 -p-cymene)Ru - L6 system also exhibited enhanced catalytic activity for ortho C-H bond arylation of 2-phenylpyridine using a variety of aryl halides. NMR and mass investigations inferred the presence of several ligand coordinated Ru(II) species, suggesting the involvement of these species in C-H bond activation reaction. Further in concurrence with the experimental findings, the density functional theory (DFT) calculations also evidenced the prominent role of 2-hydroxypyridine based ligands in Ru(II) catalyzed C-H bond arylation of 2-phenylpyridine with lower energy barrier for the C-H activation step.

Counter-Anions Rendered Weak-Interactions Perturb the Stability of Tyrosinase-Mimicked Peroxo-Dicopper(II) Active Site: Unraveling Computational Indicators.

It has been observed in literature that the stability of tyrosinase-mimicked µ-η2 :η2 -peroxo-dicopper(II) (P) can be perturbed in presence of counter-anions (CAs) such as PhCO2 - , CF3 SO3 - , TsO- and SbF6 - . In this work, we unravel computational indicators using density functional theory to screen and study the stability of P in experimentally-reported cases. These indicators are Gibbs energies, geometrical parameters such as distances and angles, independent gradient model based on Hirshfeld partition (IGMH) generated data, orbitals' overlap, and distortion-interaction (DI) energies. Our DFT computed Gibbs energies indicate that P is stable in case of PhCO2 - and TsO- . CF3 SO3 - allows P and its isoelectronic species bis-µ-oxo-dicopper (O) to coexist. SbF6 - shows that O is in excess. Our indicators reveal that the stability of P in case of PhCO2 - and TsO- is due to the better placing of P and its CA, thus leading to better interactions and overlap of orbitals. Other indicator displays that the plane of Cu2 O2 core in P is more bend in PhCO2 - and TsO- cases as compared to the plane in the other two cases. In addition, the IGMH-based indicator displays higher values in the case of PhCO2 - and TsO- than the other CAs.

Artificial intelligence-based applications in shoulder surgery leaves much to be desired: a systematic review.

Background: Artificial intelligence (AI) aims to simulate human intelligence using automated computer algorithms. There has been a rapid increase in research applying AI to various subspecialties of orthopedic surgery, including shoulder surgery. The purpose of this review is to assess the scope and validity of current clinical AI applications in shoulder surgery literature. Methods: A systematic literature review was conducted using PubMed for all articles published between January 1, 2010 and June 10, 2022. The search query used the terms as follows: (artificial intelligence OR machine learning OR deep learning) AND (shoulder OR shoulder surgery OR rotator cuff). All studies that examined AI application models in shoulder surgery were included and evaluated for model performance and validation (internal, external, or both). Results: A total of 45 studies were included in the final analysis. Eighteen studies involved shoulder arthroplasty, 13 rotator cuff, and 14 other areas. Studies applying AI to shoulder surgery primarily involved (1) automated imaging analysis including identifying rotator cuff tears and shoulder implants (2) risk prediction analyses including perioperative complications, functional outcomes, and patient satisfaction. Highest model performance area under the curve ranged from 0.681 (poor) to 1.00 (perfect). Only 2 studies reported external validation. Conclusion: Applications of AI in the field of shoulder surgery are expanding rapidly and offer patient-specific risk stratification for shared decision-making and process automation for resource preservation. However, model performance is modest and external validation remains to be demonstrated, suggesting increased scientific rigor is warranted prior to deploying AI-based clinical applications.

Risks of chronic steroid or immunosuppressive therapy on total shoulder arthroplasty patients.

Introduction: Patients on chronic corticosteroids/immunosuppressants (SI) undergoing orthopaedic surgery are at an increased risk for surgical complications and worse outcomes. However, whether or not chronic preoperative SI use increases the risk for 30-day complications in patients undergoing primary total shoulder arthroplasty (SA) has yet to be explored. Methods: From 2006 to 2019, the National Surgical Quality Improvement Program (NSQIP) database was used to identify all patients who underwent primary SA (anatomic TSA and reverse TSA). Patients were stratified into two cohorts: chronic preoperative SI users and those without use. Bivariate and multivariate analyses were utilized in this study. Results: Of the 26,979 patients who underwent primary SA, 25,656 (95.1%) patients did not have SI usage whereas 1323 (4.9%) patients had chronic preoperative SI usage. Following adjustment on multivariate analyses, compared to the non-SI usage cohort, patients who used SI had an increased risk of urinary tract infections (UTIs) (OR 1.87; p = 0.009) and septic shock (OR 7.14; p = 0.002). There were no differences in mortality between the two cohorts (p = 0.058). Discussion and Conclusion: Chronic pre-operative SI use is an independent risk factor for septic shock and UTIs following primary SA. Surgeons and patients should be aware of these risks to better inform patient counseling and surgical decision making.

Clinical Profiles, Outcomes, and Sex Differences of Patients With STEMI: Findings From the NORIN-STEMI Registry.

Background: Low- and middle-income countries account for most of the global burden of coronary artery disease. There is a paucity of data regarding epidemiology and outcomes for ST-segment elevation myocardial infarction (STEMI) patients in these regions. Objectives: The authors studied the contemporary characteristics, practice patterns, outcomes, and sex differences in patients with STEMI in India. Methods: NORIN-STEMI (North India ST-Segment Elevation Myocardial Infarction Registry) is an investigator-initiated prospective cohort study of patients presenting with STEMI at tertiary medical centers in North India. Results: Of 3,635 participants, 16% were female patients, one-third were <50 years of age, 53% had a history of smoking, 29% hypertension, and 24% diabetes. The median time from symptom onset to coronary angiography was 71 hours; the majority (93%) presented first to a non-percutaneous coronary intervention (PCI)-capable facility. Almost all received aspirin, statin, P2Y12 inhibitors, and heparin on presentation; 66% were treated with PCI (98% femoral access) and 13% received fibrinolytics. The left ventricular ejection fraction was <40% in 46% of patients. The 30-day and 1-year mortality rates were 9% and 11%, respectively. Compared with male patients, female patients were less likely to receive PCI (62% vs 73%; P < 0.0001) and had a more than 2-fold greater 1-year mortality (22% vs 9%; adjusted HR: 2.1; 95% CI: 1.7-2.7; P < 0.001). Conclusions: In this contemporary registry of patients with STEMI in India, female patients were less likely to receive PCI after STEMI and had a higher 1-year mortality compared with male patients. These findings have important public health implications, and further efforts are required to reduce these gaps.

Trustworthy Medical Image Segmentation with improved performance for in-distribution samples.

Despite the enormous achievements of Deep Learning (DL) based models, their non-transparent nature led to restricted applicability and distrusted predictions. Such predictions emerge from erroneous In-Distribution (ID) and Out-Of-Distribution (OOD) samples, which results in disastrous effects in the medical domain, specifically in Medical Image Segmentation (MIS). To mitigate such effects, several existing works accomplish OOD sample detection; however, the trustworthiness issues from ID samples still require thorough investigation. To this end, a novel method TrustMIS (Trustworthy Medical Image Segmentation) is proposed in this paper, which provides the trustworthiness and improved performance of ID samples for DL-based MIS models. TrustMIS works in three folds: IT (Investigating Trustworthiness), INT (Improving Non-Trustworthy prediction) and CSO (Classifier Switching Operation). Initially, the IT method investigates the trustworthiness of MIS by leveraging similar characteristics and consistency analysis of input and its variants. Subsequently, the INT method employs the IT method to improve the performance of the MIS model. It leverages the observation that an input providing erroneous segmentation can provide correct segmentation with rotated input. Eventually, the CSO method employs the INT method to scrutinise several MIS models and selects the model that delivers the most trustworthy prediction. The experiments conducted on publicly available datasets using well-known MIS models reveal that TrustMIS has successfully provided a trustworthiness measure, outperformed the existing methods, and improved the performance of state-of-the-art MIS models. Our implementation is available at https://github.com/SnehaShukla937/TrustMIS.