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1.
Cureus ; 16(9): e68765, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39371795

RESUMO

Internal hernias (IHs) are a rare but potentially life-threatening cause of bowel obstruction, with a high morbidity and mortality rate if not promptly diagnosed and treated. This case report highlights the clinical course of a 75-year-old female who developed a transverse mesocolic internal hernia, a subtype of transmesenteric hernia (TH), following a Hartmann reversal procedure. The patient presented to the emergency department (ED) with a sudden onset of severe, diffuse abdominal pain. Her medical history was significant for systemic lupus erythematosus, pulmonary fibrosis, multiple pulmonary embolisms, and a recent Hartmann reversal procedure the month prior. Initial imaging suggested postoperative ileus, but the patient's symptoms persisted despite conservative management. Subsequent imaging raised suspicion of an internal hernia, and on hospital day 6, an urgent diagnostic laparoscopy revealed a herniated segment of the small bowel through a defect in the transverse mesocolon with herniation into the lesser sac. The herniated bowel was successfully reduced, and the defect was repaired. The patient had an uneventful recovery and was discharged in stable condition. Transmesenteric hernias, though more common in the pediatric population, can occur in adults, particularly following abdominal surgery. Diagnosis can be challenging due to variable symptoms and imaging findings. However, prompt recognition and surgical intervention are crucial to prevent complications such as bowel ischemia and strangulation. This case underscores the importance of considering internal hernias in the differential diagnosis of small bowel obstruction (SBO), especially in patients with a history of recent abdominal surgery. Early diagnosis and timely surgical management are essential for a favorable outcome.

2.
Clin Transplant ; 38(9): e15462, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39315691

RESUMO

INTRODUCTION: Lung transplantation has become increasingly utilized in patients with COVID-19. While several single-center and UNOS database studies have been published on lung transplants (LTs) for end-stage lung disease (ESLD) from Coronavirus disease 2019 (COVID-19), there is a lack of multi-center and international data. METHODS: This is a multicenter analysis from 11 high-volume lung transplant centers in the United States and Europe. Data were collected through the Multi-Institutional ECLS Registry and stratified by ESLD due to COVID-19 versus other etiologies. Demographics and clinical variables were compared using Chi-square test and Fisher's exact test. Survival was assessed by Kaplan-Meier curves and compared by log-rank test with propensity score matching. RESULTS: Of 1606 lung transplant recipients, 46 (2.9%) were transplanted for ESLD from COVID-19 compared to 1560 (97.1%) without a history of COVID-19. Among COVID-19 patients, 30 (65.2%) had COVID-19-associated ARDS and 16 (34.8%) had post-COVID-19 fibrosis. COVID-19 patients had higher lung allocation scores (78.0 vs. 44.4, p < 0.0001), had severely limited functional status (37.0% vs. 2.9%, p < 0.0001), had higher preoperative ECMO usage (65.2% vs. 5.4%, p < 0.0001), and spent less time on the waitlist (32 vs. 137 days, p < 0.0001). A 30-day survival was comparable between COVID-19 and non-COVID-19 patients before (100% vs. 98.7%, p = 0.39) and after propensity matching (p = 0.15). CONCLUSIONS: Patients who received LTs due to COVID-19 had short-term survival comparable to that of patients without COVID-19. Our findings support the idea that lung transplantation should be considered for select patients with ESLD due to COVID-19.


Assuntos
COVID-19 , Transplante de Pulmão , Sistema de Registros , SARS-CoV-2 , Humanos , COVID-19/mortalidade , COVID-19/epidemiologia , Transplante de Pulmão/mortalidade , Masculino , Feminino , Pessoa de Meia-Idade , Estados Unidos/epidemiologia , Taxa de Sobrevida , Adulto , Europa (Continente)/epidemiologia , Estudos Retrospectivos , Idoso , Resultado do Tratamento
3.
Eur Radiol ; 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39289301

RESUMO

OBJECTIVES: The current understanding of survival prediction of lung transplant (LTx) patients with systemic sclerosis (SSc) is limited. This study aims to identify novel image features from preoperative chest CT scans associated with post-LTx survival in SSc patients and integrate them into comprehensive prediction models. MATERIALS AND METHODS: We conducted a retrospective study based on a cohort of SSc patients with demographic information, clinical data, and preoperative chest CT scans who underwent LTx between 2004 and 2020. This cohort consists of 102 patients (mean age, 50 years ± 10, 61% (62/102) females). Five CT-derived body composition features (bone, skeletal muscle, visceral, subcutaneous, and intramuscular adipose tissues) and three CT-derived cardiopulmonary features (heart, arteries, and veins) were automatically computed using 3-D convolutional neural networks. Cox regression was used to identify post-LTx survival factors, generate composite prediction models, and stratify patients based on mortality risk. Model performance was assessed using the area under the receiver operating characteristics curve (ROC-AUC). RESULTS: Muscle mass ratio, bone density, artery-vein volume ratio, muscle volume, and heart volume ratio computed from CT images were significantly associated with post-LTx survival. Models using only CT-derived features outperformed all state-of-the-art clinical models in predicting post-LTx survival. The addition of CT-derived features improved the performance of traditional models at 1-year, 3-year, and 5-year survival prediction with maximum AUC scores of 0.77 (0.67-0.86), 0.85 (0.77-0.93), and 0.90 (95% CI: 0.83-0.97), respectively. CONCLUSION: The integration of CT-derived features with demographic and clinical features can significantly improve t post-LTx survival prediction and identify high-risk SSc patients. KEY POINTS: Question What CT features can predict post-lung-transplant survival for SSc patients? Finding CT body composition features such as muscle mass, bone density, and cardiopulmonary volumes significantly predict survival. Clinical relevance Our individualized risk assessment tool can better guide clinicians in choosing and managing patients requiring lung transplant for systemic sclerosis.

4.
Bull Hosp Jt Dis (2013) ; 82(4): 261-265, 2024 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-39259952

RESUMO

BACKGROUND: The periacetabular osteotomy (PAO) was developed to treat acetabular dysplasia and avoid the progression of osteoarthritis. Prior research has correlated demographic and radiographic variables with postoperative patient outcomes but with limited focus on patient expectations and correlation with satisfaction. The purpose of this study was to determine whether any such associations exist with the PAO. METHODS: An anonymous, de-identified satisfaction survey was applied to patients undergoing a PAO between April 2017 and April 2019. Forty patients (26 females) who underwent PAOs were included in the final analysis. The average age of the cohort was 22.0 ± 5.1 years of age. All patients had a minimum of 12 months of follow-up from the date of surgery. Patient demographics, diagnosis, and complications were recorded. Radiographs were then analyzed to determine pre- and postoperative lateral center edge angle (LCEA) and Tönnis roof angle, and correlations between satisfaction and radiographic analyses were performed. Statistical analysis included non-parametric Spearman's correlation and receiver operator characteristic. Statistical significance was set at p < 0.05. RESULTS: Thirty (75%) patients were satisfied with their outcome. There were no statistically significant associations between patient age or sex and postoperative satisfaction (p > 0.05). The average LCEA was 10.9° ± 6.9° preoperatively and 26.0° ± 4.2° postoperatively with an average change of 15.1° ± 5.6°. The average Tönnis angle was 18.8° ± 3.3° preoperatively, decreasing to 11.6° ± 3.2° postoperatively with an average change of -7.2° ± 3.2°. Interobserver reliability was high, ranging from r = 0.782, p < 0.001 for postoperative Tönnis angle to r = 0.958, p < 0.001 for preoperative LCEA. Preoperative LCEA correlated positively with satisfaction, r = 0.351, p = 0.027. Logistic regression demonstrated that for every increasing degree of preoperative LCEA, odds of postoperative satisfaction increased by 1.13 (95% CI: 1.01 to 1.27), p = 0.034. CONCLUSION: This study suggests that postoperative patient satisfaction after PAO may be associated with preoperative patient demographics such as LCEA. It also suggests that more dysplastic hips may have lower rates of postoperative satisfaction than patients with less severe deformity. These associations warrant further study, which may yield prognostic value for future surgery.


Assuntos
Acetábulo , Osteotomia , Satisfação do Paciente , Humanos , Feminino , Osteotomia/métodos , Osteotomia/efeitos adversos , Masculino , Satisfação do Paciente/estatística & dados numéricos , Acetábulo/cirurgia , Acetábulo/diagnóstico por imagem , Adulto Jovem , Adulto , Resultado do Tratamento , Adolescente , Estudos Retrospectivos , Radiografia , Luxação do Quadril/cirurgia , Luxação do Quadril/diagnóstico por imagem
5.
Nature ; 2024 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-39322664

RESUMO

Despite a high response rate in chimeric antigen receptor (CAR) T cell therapy for acute lymphocytic leukaemia (ALL)1-3, approximately 50% of patients relapse within the first year4-6, representing an urgent question to address in the next stage of cellular immunotherapy. Here, to investigate the molecular determinants of ultralong CAR T cell persistence, we obtained a single-cell multi-omics atlas from 695,819 pre-infusion CAR T cells at the basal level or after CAR-specific stimulation from 82 paediatric patients with ALL enrolled in the first two CAR T ALL clinical trials and 6 healthy donors. We identified that elevated type 2 functionality in CAR T infusion products is significantly associated with patients maintaining a median B cell aplasia duration of 8.4 years. Analysis of ligand-receptor interactions revealed that type 2 cells regulate a dysfunctional subset to maintain whole-population homeostasis, and the addition of IL-4 during antigen-specific activation alleviates CAR T cell dysfunction while enhancing fitness at both transcriptomic and epigenomic levels. Serial proteomic profiling of sera after treatment revealed a higher level of circulating type 2 cytokines in 5-year or 8-year relapse-free responders. In a leukaemic mouse model, type 2high CAR T cell products demonstrated superior expansion and antitumour activity, particularly after leukaemia rechallenge. Restoring antitumour efficacy in type 2low CAR T cells was attainable by enhancing their type 2 functionality, either through incorporating IL-4 into the manufacturing process or by priming manufactured CAR T products with IL-4 before infusion. Our findings provide insights into the mediators of durable CAR T therapy response and suggest potential therapeutic strategies to sustain long-term remission by boosting type 2 functionality in CAR T cells.

7.
Inflammopharmacology ; 32(5): 3499-3519, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39126568

RESUMO

Fridericia chica is an Amazonian plant used to treat stomach disorders. However, the pharmacological activity of flavonoids in the extract has yet to be investigated. Therefore, we considered that a flavonoid-rich F. chica subfraction (FRS) has gastroprotective functions. For this, before the induction of gastric ulcers with ethanol or piroxicam, the rats received vehicle (water), omeprazole (30 mg/kg), or FRS (30 mg/kg), and the ulcer area was measured macro and microscopically, and the antisecretory action was investigated in pylorus-ligated rats. In addition, the roles of nitric oxide (NO) and nonprotein sulfhydryl compounds (NP-SH) in the gastroprotective effects of FRS were studied. FRS reduced ethanol- and piroxicam-induced ulcerations by 81% and 77%, respectively, as confirmed histologically. Antioxidant effects were observed for FRS through the maintenance of GSH and LPO levels, and the SOD and CAT activity similar to those found in the nonulcerated group. Moreover, FRS avoided the increase in MPO activity and TNF, IL-6, IL-4 and IL-10 levels. Moreover, mucin staining increased in ulcerated rats receiving FRS, and the pharmacological mechanism gastroprotective seems to involve the NO and NP-SH in addition to antisecretory actions. The chemical study by mass spectrometry confirmed the presence of flavonoids in FRS, and molecular docking studies have shown that these compounds interact with cyclooxygenase-1 and NO synthase. Furthermore, there was no indication that FRS had cytotoxic effects. Our results support the popular use of F. chica, and we conclude that the gastroprotection effect promoted by FRS can be attributed to the combined effect of the flavonoids.


Assuntos
Antiulcerosos , Antioxidantes , Flavonoides , Extratos Vegetais , Plantas Medicinais , Ratos Wistar , Úlcera Gástrica , Animais , Flavonoides/farmacologia , Flavonoides/isolamento & purificação , Úlcera Gástrica/tratamento farmacológico , Úlcera Gástrica/induzido quimicamente , Úlcera Gástrica/prevenção & controle , Ratos , Extratos Vegetais/farmacologia , Masculino , Antiulcerosos/farmacologia , Antiulcerosos/isolamento & purificação , Plantas Medicinais/química , Antioxidantes/farmacologia , Óxido Nítrico/metabolismo , Fabaceae/química , Mucosa Gástrica/efeitos dos fármacos , Mucosa Gástrica/metabolismo , Mucosa Gástrica/patologia , Simulação de Acoplamento Molecular
11.
Clin Transplant ; 38(9): e15444, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39190289

RESUMO

Persistent acute kidney injury (pAKI), compared with acute kidney injury (AKI) that resolves in <72 h, is associated with worse prognosis in critically ill patients. Definitions and prognosis of pAKI are not well characterized in solid organ transplant patients. Our aims were to investigate (a) definitions and incidence of pAKI; (b) association with clinical outcomes; and (c) risk factors for pAKI among heart, lung, and liver transplant recipients. We systematically reviewed the literature including PubMed, Embase, Web of Science, and Cochrane from inception to 8/1/2023 for human prospective and retrospective studies reporting on the development of pAKI in heart, lung, or liver transplant recipients. We assessed heterogeneity using Cochran's Q and I2. We identified 25 studies including 6330 patients. AKI (8%-71.6%) and pAKI (2.7%-55.1%) varied widely. Definitions of pAKI included 48-72 h (six studies), 7 days (three studies), 14 days (four studies), or more (12 studies). Risk factors included age, body mass index (BMI), diabetes, preoperative chronic kidney disease (CKD), intraoperative vasopressor use, and intraoperative circulatory support. pAKI was associated with new onset of CKD (odds ratio [OR] 1.41-11.2), graft dysfunction (OR 1.81-8.51), and long-term mortality (OR 3.01-13.96), although significant heterogeneity limited certainty of CKD and graft dysfunction outcome analyses. pAKI is common and is associated with worse mortality among liver and lung transplant recipients. Standardization of the nomenclature of AKI will be important in future studies (PROSPERO CRD42022371952).


Assuntos
Injúria Renal Aguda , Transplante de Órgãos , Transplantados , Humanos , Injúria Renal Aguda/epidemiologia , Injúria Renal Aguda/etiologia , Transplante de Órgãos/efeitos adversos , Complicações Pós-Operatórias/epidemiologia , Complicações Pós-Operatórias/etiologia , Prognóstico , Fatores de Risco , Transplantados/estatística & dados numéricos
12.
J Am Chem Soc ; 146(38): 25986-25999, 2024 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-39145676

RESUMO

In the pursuit of selective conversion of methane directly to methanol in the liquid-phase, a common challenge is the concurrent formation of undesirable liquid oxygenates or combustion byproducts. However, we demonstrate that monometallic Pd-CeO2 catalysts, modified by carbon, created by a simple mechanochemical synthesis method exhibit 100% selectivity toward methanol at 75 °C, using hydrogen peroxide as oxidizing agent. The solvent free synthesis yields a distinctive Pd-iC-CeO2 interface, where interfacial carbon (iC) modulates metal-oxide interactions and facilitates tandem methane activation and peroxide decomposition, thus resulting in an exclusive methanol selectivity of 100% with a yield of 117 µmol/gcat at 75 °C. Notably, solvent interactions of H2O2 (aq) were found to be critical for methanol selectivity through a density functional theory (DFT)-simulated Eley-Rideal-like mechanism. This mechanism uniquely enables the direct conversion of methane into methanol via a solid-liquid-gas process.

13.
Protein Sci ; 33(9): e5135, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39150232

RESUMO

Tardigrades are unique micro-organisms with a high tolerance to desiccation. The protection of their cells against desiccation involves tardigrade-specific proteins, which include the so-called cytoplasmic abundant heat soluble (CAHS) proteins. As a first step towards the design of peptides capable of mimicking the cytoprotective properties of CAHS proteins, we have synthesized several model peptides with sequences selected from conserved CAHS motifs and investigated to what extent they exhibit the desiccation-induced structural changes of the full-length proteins. Using circular dichroism spectroscopy, two-dimensional infrared spectroscopy, and molecular dynamics simulations, we have found that the CAHS model peptides are mostly disordered, but adopt a more α $$ \alpha $$ -helical structure upon addition of 2,2,2-trifluoroethanol, which mimics desiccation. This structural behavior is similar to that of full-length CAHS proteins, which also adopt more ordered conformations upon desiccation. We also have investigated the surface activity of the peptides at the air/water interface, which also mimics partial desiccation. Interestingly, sum-frequency generation spectroscopy shows that all model peptides are surface active and adopt a helical structure at the air/water interface. Our results suggest that amino acids with high helix-forming propensities might contribute to the propensity of these peptides to adopt a helical structure when fully or partially dehydrated. Thus, the selected sequences retain part of the CAHS structural behavior upon desiccation, and might be used as a basis for the design of new synthetic peptide-based cryoprotective materials.


Assuntos
Simulação de Dinâmica Molecular , Peptídeos , Tardígrados , Tardígrados/química , Animais , Peptídeos/química , Estrutura Secundária de Proteína , Sequência de Aminoácidos
14.
J Child Orthop ; 18(4): 393-398, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-39100982

RESUMO

Purpose: Developmental hip dysplasia is a prevalent pediatric musculoskeletal condition that lacks international standardized screening. We sought to characterize developmental hip dysplasia screening practices in countries with the top global health indices. We also explored diverse definitions in reported epidemiologic rates of this condition. Methods: We performed a scoping review of developmental hip dysplasia screening protocols utilizing countries ranked in the top 25 of the Bloomberg Global Health Index using a protocolized search strategy, progressing from academic to layperson sources. A reference was eligible for inclusion if it mentioned the countries' screening program and developmental hip dysplasia was the pathology of concern. Incidence rates, when present, were also recorded. The United States Census Bureau's International Database tool provided countries' populations. We compiled the data and performed descriptive statistics and appropriate validation methods. Results: Twenty countries (80%) had searchable screening programs. Clinical screening with selective universal screening was the most commonly observed (n = 16). Four countries had universal ultrasound screening: Switzerland, Austria, Germany, and Slovenia. Five countries did not have searchable programs. No countries employed radiographic screening. Incidence rates were expressly stated in the literature for nine countries; however, the cohort of interest varied from developmental hip dysplasia versus severity of developmental hip dysplasia versus miscellaneous (e.g. requiring hospitalization). Conclusion: The findings of this investigation highlight international inconsistencies regarding developmental hip dysplasia screening and epidemiologic data. Screening variations exist despite consensus statements calling for uniformity. We agree with prior literature advocating for increasing consistency in developmental hip dysplasia management or, at a minimum, increasing transparency regarding how we manage these young patients.

15.
Nature ; 633(8029): 318-322, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39074505

RESUMO

The first observations of the James Webb Space Telescope (JWST) have revolutionized our understanding of the Universe by identifying galaxies at redshift z ≈ 13 (refs. 1-3). In addition, the discovery of many luminous galaxies at Cosmic Dawn (z > 10) has suggested that galaxies developed rapidly, in apparent tension with many standard models4-8. However, most of these galaxies lack spectroscopic confirmation, so their distances and properties are uncertain. Here we present JWST Advanced Deep Extragalactic Survey-Near-Infrared Spectrograph spectroscopic confirmation of two luminous galaxies at z = 14.32 - 0.20 + 0.08 and z = 13.90 ± 0.17. The spectra reveal ultraviolet continua with prominent Lyman-α breaks but no detected emission lines. This discovery proves that luminous galaxies were already in place 300 million years after the Big Bang and are more common than what was expected before JWST. The most distant of the two galaxies is unexpectedly luminous and is spatially resolved with a radius of 260 parsecs. Considering also the very steep ultraviolet slope of the second galaxy, we conclude that both are dominated by stellar continuum emission, showing that the excess of luminous galaxies in the early Universe cannot be entirely explained by accretion onto black holes. Galaxy formation models will need to address the existence of such large and luminous galaxies so early in cosmic history.

16.
Mol Ecol Resour ; 24(7): e13999, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39044539

RESUMO

Bioindication, evaluating biological responses to environmental disturbances, is crucial for assessing the ecological status of an ecosystem. While historical bioindication relied on macroscopic organisms, the introduction of environmental DNA (eDNA) techniques allows the application of protists without the necessity of morphological identification. In this study, we propose a novel bioindication methodology utilizing Arcellinida, a group of top predators among protists, as bioindicators of freshwater ecosystems. For that purpose, we first characterized the Arcellinida diversity over 1 year at three different points of Lake Sanabria, an ancient glacier lake known to be subjected to anthropogenic disturbances. We compared this diversity with an undisturbed control site. Second, we characterized the Arcellinida diversity in other ecosystems to generate the ecological background to test the connectivity between them. Results indicate limited connectivity between the different ecosystems and an edge effect between terrestrial and aquatic ecosystems. Disturbed freshwater ecosystems exhibited reduced Arcellinida diversity at both specific and infraspecific levels, providing valuable insight into recent disturbances. Arcellinida-based bioindication provides a sensitive, accurate and easy-to-interpret protocol for monitoring disturbances in freshwater ecosystems. It represents a valuable tool for environmental assessments and conservation strategies.


Assuntos
DNA Ambiental , Lagos , DNA Ambiental/genética , Ecossistema , Biodiversidade , Água Doce , Amoeba/genética , Amoeba/classificação , Amoeba/fisiologia
17.
Org Biomol Chem ; 22(32): 6582-6592, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39083363

RESUMO

This communication describes a solution to the vexing problem of synthesis of 4-nitroisoxazolidine rings from cyclic nitrones and ß-nitrostyrenes. The trans-endo adduct 2 is quantitatively synthesised from E-ß-nitrostyrene under mild conditions avoiding purification, while the trans-exo adduct 4 is obtained at higher temperatures. Furthermore, a Crystallization-Induced Diastereomer Transformation (CIDT) process was used to epimerise the NO2 bond from 2 to the cis-exo adduct 3 with total conversion assisted by the para-halogen substitution of the aromatic ring without any additives. By combining these approaches, we can establish a simple synthetic methodology that allows the diastereoselective synthesis of three diastereoisomers, overcoming the previous problems described in the literature.

18.
J Thorac Dis ; 16(6): 3753-3763, 2024 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-38983164

RESUMO

Background: Endoscopic staplers are common surgical devices used for the ligation and division of vasculature in thoracic procedures. When a stapler ligates and divides pulmonary vasculature, potentially catastrophic intraoperative bleeding at the staple-line may occur. The aim of this study was to confirm the safety and discuss the utility of a two-row stapler reload, by assessing the incidence of clinically necessary intraoperative hemostatic intervention when applied to pulmonary vasculature in real-world applications. Methods: This study was designed as a prospective non-comparative registry study conducted in seven centers across the United States, to confirm the safety and performance of Signia™ Small Diameter Reloads (SDR) when used for indicated thoracic surgical procedures. The primary endpoint was the incidence of hemostatic intervention related to the ligation and division of pulmonary arteries and veins. A five-point Likert scale scored hemostasis of each SDR staple-line. Secondary endpoints included the incidence of device-related only adverse events (AEs), device deficiencies, and procedure-related hospital readmission up to and including 30 days post operation. Results: SDR was fired 302 times across pulmonary vasculature in 120 subjects. Three firings required clinically necessary hemostatic intervention for an intervention rate of 0.99% (3 of 302 firings). Moreover, 97.5% (117 of 120 subjects) had intact SDR staple-lines regardless of surgical access or stapler handle preference. Only 4 (3.3%) thoracoscopic and robotic procedures converted to open, but none were due to SDR staple-lines. There was no statistically significant difference between the Likert score of transected arteries compared to veins (P=0.61). There were no device deficiencies or device-only related AEs reported. Conclusions: In this study, the two-row stapler reloads demonstrated favorable safety and efficacy profiles when fired across hilar vessels in the thoracic space with a 99% hemostatic rate, independent of surgical access and stapler handle preference.

19.
Phys Chem Chem Phys ; 26(31): 20947-20961, 2024 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-39046374

RESUMO

We present here extensive calculations of the O(3P) + H2 and O(3P) + D2 reaction dynamics spanning the temperature range from 200 K to 2500 K. The calculations have been carried out using fully converged time-independent quantum mechanics (TI QM), quasiclassical trajectories (QCT) and ring polymer molecular dynamics (RPMD) on the two lowest lying adiabatic potential energy surfaces (PESs), 13A' and 13A'', calculated by Zanchet et al. [J. Chem. Phys., 2019, 151, 094307]. TI QM rate coefficients were determined using the cumulative reaction probability formalism on each PES including all of the total angular momenta and the Coriolis coupling and can be considered to be essentially exact within the Born-Oppenheimer approximation. The agreement between the rate coefficients calculated by using QM and RPMD is excellent for the reaction with D2 in almost the whole temperature range. For the reaction with H2, although the agreement is very good above 500 K, the deviations are significant at lower temperatures. In contrast, the QCT calculations largely underestimate the rate coefficients for the two isotopic variants due to their inability to account for tunelling. The differences found in the disagreements between RPMD and QM rate coefficients for the reactions for both the isotopologues are indicative of the ability of the RPMD method to accurately describe systems where tunelling plays a relevant role. Considering that both reactions are dominated by tunelling below 500 K, the present results show that RPMD is a very powerful tool for determining rate coefficients. The present QM rate coefficients calculated on adiabatic PESs slightly underestimate the best global fits of the experimental measurements, which we attribute to the intersystem crossing with the singlet 11A' PES.

20.
Sci Total Environ ; 949: 175077, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39074742

RESUMO

The substantial increase in the presence of greenhouse gases (GHGs) in the atmosphere has led to the development of several sampling techniques to quantify and characterize the sources of high global warming potential gas emissions. In this context, we developed a new method to estimate the time-averaged concentration of atmospheric methane that employs a long hose to collect a sample of gas by diffusion through one of its ends. We performed numerical simulations to illustrate the basis of our method and to determine the numerical factors required to estimate the time-averaged concentration of methane. This novel technique for estimating the mean gas concentration was then validated with two sets of experiments, where the source of methane was ruminant enteric fermentation measured in a respiration chamber. We compared the time-averaged methane concentration obtained with our methodology for periods (T) ranging from 1 to 4 days with those measured using the sensor of a respiration chamber. We found that the accuracy of the estimates improved as T increased from an error of 20 % for T = 1 to an error smaller than 10 % for T ≥ 2 days. In additional tests, and as suggested by numerical simulations, we confirmed that measuring and employing the methane concentration in the furthest half of the collector leads to a more precise estimation of atmospheric concentration than when the concentration of the entire collector is considered. This work demonstrates that the new methodology for air sampling, in conjunction with numerical analysis, is a viable alternative for quantifying atmospheric methane concentrations. In addition, the simple design of the devices showed remarkable benefits in terms of both the cost and simplicity for implementing large-scale individual sampling. We discuss its potential application to other GHGs.

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