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OBJECTIVE: To describe femoroacetabular posterior translation (FAPT) using dynamic hip ultrasonography (DHUS), and to determine the inter- and intra-rater reliability of hip ultrasound measurements of FAPT. MATERIALS AND METHODS: The study design was a feasibility study of 13 healthy young adults (26 hips) using test-retest analysis. The data was collected prospectively over a 2-week time period. Three DHUS measurements (posterior neutral (PN), flexion, adduction, and internal rotation (PFADIR), and stand and load (PStand) were measured by four independent raters (2 senior who divided the cohort, 1 intermediate, 1 junior) at two time points for bilateral hips of each participant. Reliability was assessed by calculating the intraclass correlation coefficient (ICC) along with 95% confidence intervals (CIs) for each rater and across all raters. RESULTS: A total of 468 US scans were completed. The mean age of the cohort was 25.7 years (SD 5.1 years) and 54% were female. The inter-rater reliability was excellent for PFADIR (ICC 0.85 95% CI 0.76-0.91), good for PN (ICC 0.69 95% CI 0.5-0.81), and good for PStand (ICC 0.72 95% CI 0.55-0.83). The intra-rater reliability for all raters was good for PFADIR (ICC 0.60 95% CI 0.44-0.73), fair for PN (ICC 0.42 95% CI 0.21-0.59), and fair for PStand (ICC 0.42 95% CI 0.22-0.59). CONCLUSION: This is the first study to present a protocol using dynamic ultrasonography to measure FAPT. DHUS measure for FAPT was shown to be reliable across raters with varying levels of ultrasound experience.
Subject(s)
Feasibility Studies , Ultrasonography , Humans , Female , Male , Reproducibility of Results , Ultrasonography/methods , Adult , Prospective Studies , Hip Joint/diagnostic imaging , Range of Motion, Articular/physiologyABSTRACT
PURPOSE: Advances in mass spectrometry-based quantitative proteomic analysis have successfully demonstrated the in-depth detection of protein biomarkers in bronchoalveolar lavage fluid (BALF) from patients with lung cancers. Recently, ion mobility technology was incorporated into the mass spectrometers escalating the sensitivity and throughput. Utilizing these advantages, herein, we employed the parallel accumulation-serial fragmentation (PASEF) implanted in a timsTOF Pro mass spectrometer to examine the alteration of BALF proteomes in patients with nonsmall cell lung cancers (NSCLCs). EXPERIMENTAL DESIGN: BALF proteins were processed from patients with NSCLC and analyzed in a timsTOF Pro mass spectrometer with the PASEF method using a peptide input of 100 ng. Label-free mass spectrometry data were analyzed in the FragPipe platform. RESULTS: We quantitated over 1400 proteins from a single injection of 100 ng of peptides per sample with a median of â¼2000 proteins. We were able to find a few potential biomarker proteins upregulated in NSCLC. CONCLUSIONS AND CLINICAL RELEVANCE: The alterations of the BALF proteome landscape vary among patients with NSCLC as previously observed in patients with small-cell lung cancers. The PASEF method has significantly enhanced the sensitivity and throughput, demonstrating its effectiveness in clinical research and application.
Subject(s)
Carcinoma, Non-Small-Cell Lung , Lung Neoplasms , Humans , Bronchoalveolar Lavage Fluid/chemistry , Lung Neoplasms/metabolism , Proteomics/methods , Mass Spectrometry , Peptides , ProteomeABSTRACT
OBJECTIVE: This systematic review and network meta-analysis (NMA) comprehensively compared the effectiveness of different mouth rinses in reducing the viral load/infectivity of severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) (Part I), alleviating clinical symptoms or severity of disease (Part II), and decreasing the incidence of SARS-CoV-2 infection (Part III). METHODS: Randomized controlled trials (RCTs) and non-randomized controlled trials (NRCTs) with restrictions were searched up to 3rd March 2023. Twenty-three studies (22 RCTs and one NRCT) met the inclusion criteria for this systematic review. RESULTS: Five RCTs (454 patients and nine interventions) in Part I were eligible for NMA. The NMA results showed that, in comparison with no rinse, sodium chloride (NaCl) was the most effective mouth rinse for reducing the viral load, followed by povidone-iodine (PVP-I), ß-cyclodextrin + citrox (CDCM), hydrogen peroxide (HP), chlorhexidine gluconate (CHX), cetylpyridinium chloride (CPC), placebo and hypochlorous acid (HClO). However, these results were not significant. Based on surface under the cumulative ranking curve scores, PVP-I was likely to be the most efficacious mouth rinse for reducing SARS-CoV-2 viral load, followed by CDCM, HP, NaCl, CHX, CPC, placebo, no rinse and HClO. CONCLUSION: Due to heterogeneity of the primary studies, the effectiveness of different mouth rinses to reduce viral infectivity, improve clinical symptoms or prevent SARS-CoV-2 infection remains inconclusive.
Subject(s)
COVID-19 , Humans , Mouthwashes/therapeutic use , Povidone-Iodine , SARS-CoV-2 , Sodium Chloride/therapeutic use , Network Meta-Analysis , Hydrogen Peroxide , MouthABSTRACT
Technological developments and improvements in single-cell isolation and analytical platforms allow for advanced molecular profiling at the single-cell level, which reveals cell-to-cell variation within the admixture cells in complex biological or clinical systems. This helps to understand the cellular heterogeneity of normal or diseased tissues and organs. However, most studies focused on the analysis of nucleic acids (e.g., DNA and RNA) and mass spectrometry (MS)-based analysis for proteins and metabolites of a single cell lagged until recently. Undoubtedly, MS-based single-cell analysis will provide a deeper insight into cellular mechanisms related to health and disease. This review summarizes recent advances in MS-based single-cell analysis methods and their applications in biology and medicine.
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PURPOSE: Small cell lung cancer (SCLC) is one of the malignant cancers with aggressive progression and poor prognosis. Bronchoalveolar lavage fluid (BALF) has been arising recently as a potential source of biomarkers for lung cancers. In this study, we performed quantitative BALF proteomic analysis to identify potential biomarkers for SCLC. EXPERIMENTAL DESIGN: BALF were collected from tumor-bearing lungs and non-tumor lungs of five SCLC patients. Then, BALF proteomes were prepared for a TMT-based quantitative mass spectrometry analysis. Differentially expressed proteins (DEP) were identified when considering individual variation. Potential SCLC biomarker candidates were validated by immunohistochemistry (IHC). A public database of multiple SCLC cell lines was used to evaluate the correlation of these markers with SCLC subtypes and chemo-drug responses. RESULTS: We identified 460 BALF proteins in SCLC patients and observed considerable individual variation among the patients. Immunohistochemical analysis and bioinformatics resulted in the identification of CNDP2 and RNPEP as potential subtype markers for ASCL1 and NEUROD1, respectively. In addition, CNDP2 was found to be positively correlated with responses to etoposide, carboplatin, and irinotecan. CONCLUSIONS AND CLINICAL RELEVANCE: BALF is an emerging source of biomarkers, making it useful for the diagnosis and prognosis of lung cancers. We characterized the proteomes of paired BALF samples collected from tumor-bearing and non-tumor lungs of SCLC patients. Several proteins were found elevated in tumor-bearing BALF, and especially CNDP2 and RNPEP appeared to be potential indicators for ASLC1-high and NEUROD1-high subtypes of SCLC, respectively. The positive correlation of CNDP2 with chemo-drug responses would help to make decisions for treatment of SCLC patients. These putative biomarkers could be comprehensively investigated for a clinical use towards precision medicine.
Subject(s)
Lung Neoplasms , Small Cell Lung Carcinoma , Humans , Small Cell Lung Carcinoma/diagnosis , Bronchoalveolar Lavage Fluid , Proteomics , Proteome , Biomarkers, Tumor/metabolism , Lung Neoplasms/metabolismABSTRACT
In 2019, a community-based, cross-sectional carriage survey and a seroprevalence survey of 1,216 persons 1-55 years of age were conducted in rural Vietnam to investigate the mechanism of diphtheria outbreaks. Seroprevalence was further compared with that of an urban area that had no cases reported for the past decade. Carriage prevalence was 1.4%. The highest prevalence, 4.5%, was observed for children 1-5 years of age. Twenty-seven asymptomatic Coerynebacterium diphtheriae carriers were identified; 9 carriers had tox gene-bearing strains, and 3 had nontoxigenic tox gene-bearing strains. Child malnutrition was associated with low levels of diphtheria toxoid IgG, which might have subsequently increased child carriage prevalence. Different immunity patterns in the 2 populations suggested that the low immunity among children caused by low vaccination coverage increased transmission, resulting in symptomatic infections at school-going age, when vaccine-induced immunity waned most. A school-entry booster dose and improved infant vaccination coverage are recommended to control transmissions.
Subject(s)
Corynebacterium diphtheriae , Diphtheria , Child , Infant , Humans , Diphtheria/epidemiology , Diphtheria/prevention & control , Seroepidemiologic Studies , Cross-Sectional Studies , Vietnam/epidemiology , Corynebacterium , Vaccination , Corynebacterium diphtheriae/geneticsABSTRACT
PURPOSE: Data regarding the health-related quality of life (HRQoL) in men and women after percutaneous coronary intervention (PCI) in low-and-middle incomes countries remains scarce. To investigate sex difference in the HRQoL at 30 days and 12 months post PCI in Vietnam. METHODS: We used data from a single percutaneous coronary registry established in the Vietnam National Heart Institute. The HRQoL was measured using the EQ-5D-3L instrument via telephone interviews, and information about demographics, clinical presentation and procedures was obtained through face-to-face interviews and medical records. The HRQoL between men and women were compared using independent samples t tests, the Mann-Whitney U test or univariate/multivariate logistic regression. RESULTS: There were 866 patients included in this cohort, with the proportion of women being nearly half of men (32.1 vs 67.9%). Women were 3.5 years older, had lower income and educational levels but greater prevalence of cardiovascular risk factors. At 30 days, women significantly had more problems in mobility, personal care and pain/discomfort compared to men. At 12 months, women had more problem than men in usual activity. The geometric means of HRQoL was lower in women at 30 days, but not in 12 months. From 30 days to 12 months after discharge, women showed better recovery in mobility compared to men, but not in other dimensions. CONCLUSIONS: In this first insight of sex differences in HRQoL following PCI in Vietnam, women appeared to have worse quality of life, especially at 30 days after discharge but they showed better recovery in mobility at 12 months compared to men.
Subject(s)
Percutaneous Coronary Intervention , Quality of Life , Humans , Female , Male , Quality of Life/psychology , Sex Characteristics , Percutaneous Coronary Intervention/adverse effects , Vietnam , Self CareABSTRACT
Prussian blue analogues (PBAs) are archetypes of microporous coordination polymers/metal-organic frameworks whose versatile composition allows for diverse functionalities. However, developments in PBAs have centred solely on their crystalline state, and the glassy state of PBAs has not been explored. Here we describe the preparation of the glassy state of PBAs via a mechanically induced crystal-to-glass transformation and explore their properties. The preservation of short-range metal-ligand-metal connectivity is confirmed, enabling the framework-based functionality and semiconductivity in the glass. The transformation also generates unconventional CN- vacancies, followed by the reduction of metal sites. This leads to significant porosity enhancement in recrystallised PBA, enabled by further accessibility of isolated micropores. Finally, mechanical stability under stress for successful vitrification is correlated to defect contents and interstitial water. Our results demonstrate how mechanochemistry provides opportunities to explore glassy states of molecular framework materials in which the stable liquid state is absent.
ABSTRACT
OBJECTIVE: BTO is the procedure performed to assess the collateral circulation within the Willis circle in a giant ICA aneurysm. An ICA occlusion after BTO is very rare. We present a case of an internal carotid artery occlusion as a complication of BTO that required urgent revascularization surgery. CASE PRESENTATION: A 56-year-old female with a history of transient ischemic attacks for one year was diagnosed with multiple aneurysms: a giant aneurysm of the left supra-clinoid ICA, two small ones on left MCA and right ophthalmic. A BTO was performed to assess collateral supply and determine whether bypass surgery should be necessary. During the procedure, the balloon was detached while insufflating, and the patient had a subsequent neurological decline consistent with an MCA syndrome. EC-IC bypass surgery was performed with an end-to-side anastomosis of STA-MCA by trapping the giant aneurysm and clipping the ipsilateral MCA aneurysm. The patient had a reversal of neurological symptoms and made an uneventful recovery. DISCUSSION: We discuss the epidemiology of giant ICA aneurysms, the indications for BTO, and its complication. Emergency intracranial and extracranial bypass surgery in case of acute ICA injury is also discussed. We also highlighted the attributable factors to treatment strategies under restrictive conditions in Vietnam. CONCLUSIONS: ICA occlusion due to insufflated balloon detachment is an unreported complication in literature. Emergency bypass surgery is a potential treatment choice for this unusual iatrogenic complication.
ABSTRACT
Identifying collective variables (CVs) for chemical reactions is essential to reduce the 3N-dimensional energy landscape into lower dimensional basins and barriers of interest. However, in condensed phase processes, the nonmeaningful motions of bulk solvent often overpower the ability of dimensionality reduction methods to identify correlated motions that underpin collective variables. Yet solvent can play important indirect or direct roles in reactivity, and much can be lost through treatments that remove or dampen solvent motion. This has been amply demonstrated within principal component analysis (PCA), although less is known about the behavior of nonlinear dimensionality reduction methods, e.g., uniform manifold approximation and projection (UMAP), that have become recently utilized. The latter presents an interesting alternative to linear methods though often at the expense of interpretability. This work presents distance-attenuated projection methods of atomic coordinates that facilitate the application of both PCA and UMAP to identify collective variables in the presence of explicit solvent and further the specific identity of solvent molecules that participate in chemical reactions. The performance of both methods is examined in detail for two reactions where the explicit solvent plays very different roles within the collective variables. When applied to raw molecular dynamics data in solution, both PCA and UMAP representations are dominated by bulk solvent motions. On the other hand, when applied to data preprocessed by our attenuated projection methods, both PCA and UMAP identify the appropriate collective variables (though varying sensitivity is observed due to the presence of explicit solvent that results from the projection method). Importantly, this approach allows identification of specific solvent molecules that are relevant to the CVs and their importance.
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OBJECTIVE: Hallux sesamoid injuries are well described and can be debilitating and chronically disabling. The role of orthobiologics such as platelet-rich plasma (PRP) in sesamoid injuries has not been reported. This study describes three cases of recalcitrant hallux sesamoid injuries in teenage athletes who returned to impact activities, pain free, following one treatment of PRP. METHODS: This is a case-series study describing three teenage athletes presenting to a tertiary level pediatric sports medicine practice with chronic hallux sesamoid injuries. RESULTS: The three patients (two female, one male) described in this case series were 13-, 16-, and 17-year-old athletes. Their primary sports were ballet, basketball, and Irish step dance, respectively. All three athletes received PRP: two received unilateral treatment (one tibial sesamoid, one fibular sesamoid) and one received treatment to bilateral tibial sesamoids. The average duration of symptoms prior to PRP was 52.5 weeks (14-128 weeks). The average time out of their primary sport was 48.7 weeks (20-78 weeks). Three of the 4 sesamoids treated with PRP were tibial sesamoids. Each site of injury was treated with one treatment of leukocyte-rich PRP. All three athletes were cleared to return to impact activities such as running and jumping at 6-9 weeks following PRP, specifically 9 weeks after the final PRP injection for the patient who underwent bilateral treatments. CONCLUSION: In the three cases provided of sesamoid injuries treated with PRP, the time to return to impact activities was less than reported for athletes not treated with PRP. Acknowledging that other management factors likely contributed to return to impact activities, this case series sets the groundwork for future research investigating the role of PRP with needle fenestration in the treatment of sesamoid injuries.
Subject(s)
Dancing , Hallux , Platelet-Rich Plasma , Running , Sesamoid Bones , Adolescent , Athletes , Child , Dancing/injuries , Female , Humans , Male , Sesamoid Bones/diagnostic imaging , Sesamoid Bones/injuriesABSTRACT
Children represent a small fraction of total cumulative cases of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection. The potential health consequences related to infection for children are not inconsequential. For example, some may develop multisystem inflammatory syndrome in children, which is commonly associated with cardiovascular involvement. Nevertheless, the short- and long-term effects of SARS-CoV-2 infection remain unknown. In particular, the impact on physical health and how it affects one's ability to return to physical activity are continuously evolving. As more youth sports organizations are lifting restrictions, the volume of youth athletes will increase and the demand for providing medical clearance will grow. This article aims to provide a review of return to physical activity guidelines for young athletes post-SARS-CoV-2 infection based on expert consensus statements and professional organization recommendations. [Pediatr Ann. 2021;50(11):e461-e464.].
Subject(s)
Athletes/psychology , COVID-19/prevention & control , Return to Sport , Youth Sports , Adolescent , COVID-19/complications , COVID-19/epidemiology , COVID-19/psychology , Child , Humans , SARS-CoV-2 , Systemic Inflammatory Response SyndromeABSTRACT
ABSTRACT: The spontaneous regression of an osteochondroma is extremely rare. We report a case of medial femoral condyle impaction fracture over the site of spontaneous regression of a pedunculated osteochondroma discovered on advanced imaging after an acute injury in a 16-year-old male American football athlete. Although spontaneous regression of an osteochondroma has been described, the case presented reveals questions regarding resultant architectural changes to the bone after resorption, leaving it prone to injury. This is the first case that describes increased injury risk potential at the site of osteochondral regression.
Subject(s)
Bone Neoplasms , Femoral Fractures , Femur/injuries , Osteochondroma , Adolescent , Athletes , Bone Neoplasms/diagnostic imaging , Humans , Male , Osteochondroma/diagnostic imagingABSTRACT
A fluorescent paper strip immunoassay in conjunction with carbon nanodots@silica (CND@SiO2) as a label was developed for the quantitative measurements of human serum amyloid A1 (hSAA1) in serum at clinically significant concentrations for lung cancer diagnosis. Monodispersed CND@SiO2 was prepared by cohydrolysis between silane-crosslinked carbon nanodots and silica precursors via the Ströber method and further attached covalently to anti-hSAA1 (14F8) monoclonal antibody [anti-hSAA1(14F8)] specific to the hSAA1 target. The hSAA1 concentrations were then determined by quantifying the blue fluorescence intensity upon 365 nm excitation of the captured hSAA1 with anti-hSAA1(14F8)-CND@SiO2 conjugates in the test line on a paper strip where anti-hSAA1 (10G1) monoclonal antibody was physisorbed. The developed fluorescent paper strip with CND@SiO2 can detect hSAA1 at concentrations ranging from 0.1 to 5 nM (R2 = 0.995), with a limit of detection of 0.258 nM in 10 mM phosphate buffer pH 7.4 containing human serum albumin. The performance of recovery (90.98-109.17%) and repeatability (coefficients of variation < 8.46%) obtained was also acceptable for quantitative determinations. The platform was employed for direct determination of hSAA1 concentrations in undiluted serum samples from lung cancer patients (relative standard deviation (RSD) < 7.46%) and healthy humans (RSD < 3.96%). The results were compared with those obtained using a commercially available enzyme-linked immunosorbent assay alongside liquid chromatography with tandem mass spectrometry measurements.
Subject(s)
Carbon/chemistry , Immunoassay/methods , Serum Amyloid A Protein/metabolism , Silicon Dioxide/chemistry , Fluorescence , HumansABSTRACT
The optimal screening strategy to prevent sudden cardiac death (SCD) in athletes remains unknown. Pre-participation screening with electrocardiogram (ECG) remains controversial. The utility and accuracy of limb-lead (LL) ECG alone in identifying cardiac abnormalities associated with SCD has not been studied. This study was a comparative secondary data analysis, comparing the interpretation accuracy of 4 physicians evaluating publicly available ECGs of the most common cardiac conditions associated with SCD in athletes. Each physician interpreted a total of 100 ECGs: 50 normal ECGs (25 LL and 25 standard 12L) and 50 abnormal ECGs (25 LL and 25 standard 12L). The agreement between LL ECGs and 12L ECGs was assessed by Cohen's kappa coefficient and the accuracy of identifying an abnormal ECG was compared across LL and 12L ECGs using a chi-squared test. Inter-rater reliability was assessed by estimating the Fleiss's kappa coefficient. The sensitivity of LL ECG and 12L ECG was identical at 86%. The specificity of LL ECG was 75% (95% CI = 65% to 83%) and 12L ECG was 82% (95% CI = 73% to 89%). Substantial agreement was seen between LL ECG and 12L ECG interpretation across all readers (k = 0.63; 95% CI = 0.49 to 0.77). Interpretation accuracy was 81% (95% CI = 74% to 86%) and 84% (95% CI 78% to 89%) using LL ECG and 12L ECG, respectively (p = 0.43). In conclusion, the accuracy, sensitivity, and specificity were high and comparable for both LL ECG and 12L ECG in identifying cardiovascular conditions associated with SCD. Agreement between LL ECG and 12L ECG was substantial.
Subject(s)
Athletes , Cardiovascular Diseases/diagnosis , Death, Sudden, Cardiac/prevention & control , Electrocardiography/methods , Arrhythmogenic Right Ventricular Dysplasia/complications , Arrhythmogenic Right Ventricular Dysplasia/diagnosis , Arrhythmogenic Right Ventricular Dysplasia/physiopathology , Brugada Syndrome/complications , Brugada Syndrome/diagnosis , Brugada Syndrome/physiopathology , Cardiomyopathy, Dilated/complications , Cardiomyopathy, Dilated/diagnosis , Cardiomyopathy, Dilated/physiopathology , Cardiomyopathy, Hypertrophic/complications , Cardiomyopathy, Hypertrophic/diagnosis , Cardiomyopathy, Hypertrophic/physiopathology , Cardiovascular Diseases/complications , Cardiovascular Diseases/physiopathology , Death, Sudden, Cardiac/etiology , Humans , Long QT Syndrome/complications , Long QT Syndrome/diagnosis , Long QT Syndrome/physiopathology , Mass Screening , Myocarditis/complications , Myocarditis/diagnosis , Myocarditis/physiopathology , Wolff-Parkinson-White Syndrome/complications , Wolff-Parkinson-White Syndrome/diagnosis , Wolff-Parkinson-White Syndrome/physiopathologyABSTRACT
BACKGROUND: Little is known about rates of access site (transradial (TRI) or transfemoral (TFI)) preference for percutaneous coronary intervention (PCI) and in-hospital costs of patients undergoing these procedures in lower-and middle-countries. Here, we report on access site use, in-hospital costs and outcomes of patients undergoing PCI in Vietnam. METHODS: Information from 868 patients were included in the cohort of 1022 patients recruited into the first PCI registry in Vietnam. The total hospital costs and in-hospital outcomes of patients undergoing TRI and TFI were compared. Hospital costs were obtained from the hospital admission system, and major adverse cardiac events, major bleeding events and length of stay were identified through review of medical records. FINDINGS: TRI was the dominant access site for interventionists (694/868 patients). The TFI group reported more lesions of the left main artery, more previous coronary artery bypass grafts and previous PCI in comparison with the TRI group (all p < 0.05). The TRI group was associated with a lower overall cost of admission (the adjusted difference was -1526.3 USD, 95% confident interval CI (-1996.2; -1056.3), shorter length of hospital stay (-2 days, CI (-2.8; -1.2)) and lower rates of major bleeding post-procedure. Procedural factors such as radial access site, left main disease, PCI ≥2 stents, and PCI ≥ 2 lesions having the most impact on the in-hospital cost of patients undergoing PCI. INTERPRETATIONS: Among patients undergoing PCI, TRI was associated with lower costs and favourable clinical outcomes relative to TFI. FUNDING: This research received partial financial support from Curtin University, Australia.
ABSTRACT
BACKGROUND: Evidence regarding the outcomes of percutaneous coronary intervention (PCI) in low-and-middle incomes countries remains limited. OBJECTIVES: To report the outcomes post PCI at discharge, 30 days and 12 months in Vietnam and identify the key factors associated with adverse outcomes at 12 months. METHODS: We used data from a single centre prospective cohort in Vietnam. Data regarding demographics, clinical presentation, procedural information, and outcomes of patients were collected and analysed. Primary outcomes were mortality and major adverse cardiac and cerebrovascular events. RESULTS: In total, 926 patients were included. Poor outcomes were relatively low in those undergoing PCI. Predictors of mortality and major adverse cardiac and cerebrovascular events at 12 months post-PCI included being older than 75, being male, having acute myocardial infarction, left ventricular ejection fraction ≤ 40%, prior cerebral vascular disease and having an unsuccessful PCI. CONCLUSIONS: Adverse outcomes of patients undergoing PCI in Vietnam are relatively low in comparison with those reported in other countries across the Asia Pacific region. Identification of factors associated with poor outcomes is beneficial for improving the quality of cardiac care and developing the prediction model of outcomes post-PCI in Vietnam.
Subject(s)
Coronary Artery Disease , Percutaneous Coronary Intervention , Asian People , Humans , Male , Prospective Studies , Risk Factors , Stroke Volume , Treatment Outcome , Ventricular Function, LeftABSTRACT
Umbrella-sampling density functional theory molecular dynamics (DFT-MD) has been employed to study the full catalytic cycle of the allylic oxidation of cyclohexene using a Cu(ii) 7-amino-6-((2-hydroxybenzylidene)amino)quinoxalin-2-ol complex in acetonitrile to create cyclohexenone and H2O as products. After the initial H-atom abstraction step, two different reaction pathways have been identified that are distinguished by the participation of alkyl hydroperoxide (referred to as the "open" cycle) versus the methanol side-product (referred to as the "closed" cycle) within the catalyst recovery process. Importantly, both pathways involve dehydrogenation and re-hydrogenation of the -NH2 group bound to the Cu-site - a feature that is revealed from the ensemble sampling of configurations of the reactive species that are stabilized within the explicit solvent environment of the simulation. Estimation of the energy span from the experimental turnover frequency yields an approximate value of 22.7 kcal mol-1 at 350 K. Whereas the closed cycle value is predicted to be 26.2 kcal mol-1, the open cycle value at 16.5 kcal mol-1. Both pathways are further consistent with the equilibrium between Cu(ii) and Cu(iii) that has previously been observed. In comparison to prior static DFT calculations, the ensemble of both solute and solvent configurations has helped to reveal a breadth of processes that underpin the full catalytic cycle yielding a more comprehensive understanding of the importance of radical reactions and catalysis recovery.