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Background: Traditionally, serum carbohydrate antigen 19-9 (CA 19-9) has been used as a key biomarker for pancreatic cancer and recently other biomarkers which reflect the systemic immune and inflammatory responses also have been explored as potential prognostic factors. The study aims to evaluate the significance of pretreatment neutrophil-to-lymphocyte ratio (NLR) and serum CA 19-9 as prognostic factor in pancreatic cancer patients. Methods: A retrospective analysis was conducted in 153 consecutive patients with pancreatic cancer in Instituto Nacional de Cancerología from 2013 to 2018. Pretreatment NLR and serum CA 19-9 values were recorded as well as survivals. Results: The cut-off value determined for NLR was 2.4 and for serum CA 19-9 was 553 U/mL. Survival analysis showed that the 5-year overall survival (OS) was 9% in patients with low-NLR compared with 2% for patients with high-NLR (P=0.008), and 5-year progression-free survival (PFS) was 5.7% in patients with low-NLR compared with 1.3% in patients with high-NLR (P=0.007). For patients with low-CA 19.9, 5-year OS was 8.5% compared with 0% for patients with high-CA 19-9 (P=0.002), and 5-year PFS was 4.1% in patients with low-CA 19-9 compared with 0% in patients with high-CA 19-9 (P=0.005). Classification groups created showed that 5-year OS in Group 1 (low-NLR and low-CA 19-9) was 11.8% compared with 1.9% for patients in Group 2 (either one or both high-NLR or CA 19-9) (P<0.001), and 5-year PFS was 8.6% in Group 1 and 0% in Group 2 (P=0.001). Conclusions: High-NLR and high-CA 19-9 values used separately are both independently associated with worse OS and PFS in patients with pancreatic cancer. The classification groups created combining both biomarkers showed better prognostic significance than when used separately as demonstrated by survival analysis and multivariate analysis.
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In veterinary medicine, especially within large animal medical and surgical clinics, addressing cavitary defects is a primary concern. In bovines, umbilical hernias are the most common defect, and surgical repair often necessitates the use of prosthetic materials. However, there is a high rate of recurrence with sutures or synthetic meshes, largely due to tissue contamination. The development of biological patches for such repairs is still in its early stages in veterinary medicine, with no commercially tested prototypes available in Argentina. Tissues derived from the extracellular matrix are considered for this purpose, with bovine pericardium standing out due to its architectural characteristics and mechanical properties. For an ideal membrane, the pericardium must retain its biomechanical properties while being unreactive and safe for the host. This study aimed to biomechanically and histologically characterize a bovine pericardium patch through all stages of processing. The treatment involved fixation with 0.5â¯% glutaraldehyde, immersion in an antibiotic/antimycotic solution, and detoxification and storage in a 98â¯% sterile glycerin solution, with three sodium phosphate-buffered washes between steps. Histological examinations and stress-strain tests were performed at each processing stage, using native pericardium as a control. Despite some minor modifications in the histological and mechanical properties, the final patches appear to be a viable alternative for resolving cavitary defects.
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Over half of spinal cord injury (SCI) patients develop opioid-resistant chronic neuropathic pain. Safer alternatives to opioids for treatment of neuropathic pain are gabapentinoids (e.g., pregabalin and gabapentin). Clinically, gabapentinoids appear to amplify opioid effects, increasing analgesia and overdose-related adverse outcomes, but in vitro proof of this amplification and its mechanism are lacking. We previously showed that after SCI, sensitivity to opioids is reduced by fourfold to sixfold in rat sensory neurons. Here, we demonstrate that after injury, gabapentinoids restore normal sensitivity of opioid inhibition of cyclic AMP (cAMP) generation, while reducing nociceptor hyperexcitability by inhibiting voltage-gated calcium channels (VGCCs). Increasing intracellular Ca2+ or activation of L-type VGCCs (L-VGCCs) suffices to mimic SCI effects on opioid sensitivity, in a manner dependent on the activity of the Raf1 proto-oncogene, serine/threonine-protein kinase C-Raf, but independent of neuronal depolarization. Together, our results provide a mechanism for potentiation of opioid effects by gabapentinoids after injury, via reduction of calcium influx through L-VGCCs, and suggest that other inhibitors targeting these channels may similarly enhance opioid treatment of neuropathic pain.
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Analgésicos Opioides , AMP Cíclico , Gabapentina , Neuralgia , Transdução de Sinais , Traumatismos da Medula Espinal , Animais , Neuralgia/tratamento farmacológico , Neuralgia/metabolismo , AMP Cíclico/metabolismo , Ratos , Traumatismos da Medula Espinal/tratamento farmacológico , Traumatismos da Medula Espinal/metabolismo , Analgésicos Opioides/farmacologia , Gabapentina/farmacologia , Transdução de Sinais/efeitos dos fármacos , Ratos Sprague-Dawley , Masculino , Canais de Cálcio Tipo L/metabolismo , Cálcio/metabolismo , Pregabalina/farmacologia , Pregabalina/uso terapêutico , Sinergismo Farmacológico , Células Receptoras Sensoriais/metabolismo , Células Receptoras Sensoriais/efeitos dos fármacosRESUMO
Precision-cut liver slices (PCLS) are tissue explants extensively used as an ex vivo model for metabolism and toxicity studies. When in vitro assays are conducted, it is imperative to perform a histomorphological evaluation as part of the viability analyses throughout the assay time. It is considered that good quality PCLS histological sections are difficult to obtain because they are hard to manipulate, and may shrink or fold during processing. Moreover, bibliography is not detailed on the embedding processes used. In this article, we propose an adjusted and rapid method for paraffin embedding of PCLS from crossbreed steers. Each PCLS was covered with a piece of gauze and placed into a histological cassette. These cassettes were submitted to a series of baths: 80â¯% ethanol for 10â¯min; 3 baths of 96â¯% ethanol for 10â¯min; 3 baths of butanol for 10â¯min; 1 bath of butanol-paraffin (1:1) for 20â¯min in a 60 °C laboratory oven; and 3 baths of paraffin for 20â¯min in a 60 °C laboratory oven. Folded paper boxes were used to produce paraffin blocks. It was possible to obtain complete sections with preserved cell morphology and no artifacts, and tissue appearance was similar to previous PCLS processed through the routine protocol, demonstrating the adequacy of the method implemented.
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Fígado , Inclusão em Parafina , Inclusão em Parafina/métodos , Fígado/citologia , Animais , Bovinos , Parafina , MasculinoRESUMO
The ID10 beamline of the SESAME (Synchrotron-light for Experimental Science and Applications in the Middle East) synchrotron light source in Jordan was inaugurated in June 2023 and is now open to scientific users. The beamline, which was designed and installed within the European Horizon 2020 project BEAmline for Tomography at SESAME (BEATS), provides full-field X-ray radiography and microtomography imaging with monochromatic or polychromatic X-rays up to photon energies of 100â keV. The photon source generated by a 2.9â T wavelength shifter with variable gap, and a double-multilayer monochromator system allow versatile application for experiments requiring either an X-ray beam with high intensity and flux, and/or a partially spatial coherent beam for phase-contrast applications. Sample manipulation and X-ray detection systems are designed to allow scanning samples with different size, weight and material, providing image voxel sizes from 13â µm down to 0.33â µm. A state-of-the-art computing infrastructure for data collection, three-dimensional (3D) image reconstruction and data analysis allows the visualization and exploration of results online within a few seconds from the completion of a scan. Insights from 3D X-ray imaging are key to the investigation of specimens from archaeology and cultural heritage, biology and health sciences, materials science and engineering, earth, environmental sciences and more. Microtomography scans and preliminary results obtained at the beamline demonstrate that the new beamline ID10-BEATS expands significantly the range of scientific applications that can be targeted at SESAME.
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The phase problem in the context of focusing synchrotron beams with X-ray lenses is addressed. The feasibility of retrieving the surface error of a lens system by using only the intensity of the propagated beam at several distances is demonstrated. A neural network, trained with a few thousand simulations using random errors, can predict accurately the lens error profile that accounts for all aberrations. It demonstrates the feasibility of routinely measuring the aberrations induced by an X-ray lens, or another optical system, using only a few intensity images.
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Acute kidney injury (AKI) is a highly prevalent and a critical complication of cardiac surgery (CS). Serum lactate (sLac) levels have consistently shown an association with morbimortality after CS. We performed a cross-sectional study including 264 adult patients that had a cardiac surgery between January and December 2020. Logistic regression analysis was performed to determine factors associated with AKI development. We measured the postoperative levels of sLac for all participants immediately after CS (T0) and at 4 h (T4) after the surgical intervention. A linear regression model was used to identify the factors influencing both sLac metrics. We identified four risk predictors of AKI; one was preoperative (atrial fibrillation), one intraoperative (cardiopulmonary bypass time), and two were postoperative (length of hospital stay and postoperative sLac). T0 and T4 sLac levels were higher among CS-AKI patients than in Non-CS-AKI patients. Postoperative sLac levels were significant independent predictors of CSA-AKI, and sLac levels are influenced by length of hospital stay, the number of transfused packed red blood cells, and the use of furosemide in CS-AKI patients. These findings may facilitate the earlier identification of patients susceptible to AKI after CS.
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One challenge in predicting soil parameters using in situ visible and near infrared spectroscopy is the distortion of the spectra due to soil moisture. External parameter orthogonalization (EPO) is a mathematical method to remove unwanted variability from spectra. We created two different EPO correction matrices based on the difference between spectra collected in situ and, respectively, spectra collected from the same soil samples after drying and sieving and after drying, sieving and finely grinding. Spectra from 134 soil samples recorded with two different spectrometers were split into calibration and validation sets and the two EPO corrections were applied. Clay, organic carbon and total nitrogen content were predicted by partial least squares regression for uncorrected and EPO-corrected spectra using models based on the same type of spectra ("within domain") as well as using laboratory-based models to predict in situ collected spectra ("cross-domain"). Our results show that the within-domain prediction of clay is improved with EPO corrections only for the research grade spectrometer, with no improvement for the other parameters. For the cross-domain predictions, there was a positive effect from both EPO corrections on all parameters. Overall, we also found that in situ collected spectra provided an equally successful prediction as laboratory-based spectra.
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BACKGROUND: Musculoskeletal disorders are an important cause of work absence. Clinical practice guidelines recommend nonsteroidal anti-inflammatory drugs (NSAIDs) for grade I-II cervical sprains. The combination of thiamine + pyridoxine + cyanocobalamin vitamins has been used, alone and in combination with NSAIDs, for pain and inflammation in musculoskeletal disorders. OBJECTIVE: The objective of this study was to demonstrate the analgesic synergy of dexketoprofen, and the combination of vitamins thiamine + pyridoxine + cyanocobalamin in a fixed-dose combination (FDC) for the treatment of acute pain caused by grade I-II cervical sprains. METHODS: We conducted a multicentre, prospective, randomized, double-blind, phase IIIb clinical study comparing two treatment groups: (1) dexketoprofen 25 mg/vitamin B (thiamine 100 mg, pyridoxine 50 mg and cyanocobalamin 0.50 mg) in an FDC (two or more active ingredients combined in a single dosage form) versus (2) dexketoprofen 25 mg monotherapy (single drug to treat a particular disease), one capsule or tablet orally, every 8 h for 7 days. Final mean, average change, and percentage change in pain perception (measured using a visual analogue scale [VAS]) were compared with baseline between groups. A p value < 0.05 was considered statistically significant. Analyses were conducted using SPSS software, v.29.0. RESULTS: A statistically significant reduction in pain intensity was observed from the third day of treatment with the FDC compared with monotherapy (- 3.1 ± - 1.5 and - 2.6 ± - 1.1 cm, respectively) measured using the VAS (p = 0.011). Regarding the degree of disability, using the Northwick Park Neck Pain Questionnaire (NPQ), statistical difference was observed for the final measurement (7.5%, interquartile range [IQR] 2.5, 10.5; vs. 7.9%, IQR 5.0, 13.8; p = 0.028). A lower proportion of adverse events was reported when using the FDC. CONCLUSIONS: The FDC of dexketoprofen/thiamine + pyridoxine + cyanocobalamin vitamins demonstrated superior efficacy and a better safety profile compared with dexketoprofen monotherapy for pain treatment in patients with grade I-II cervical sprains. CLINICAL TRIALS REGISTRATION: NCT05001555, registered 29 July 2021 ( https://clinicaltrials.gov/study/NCT05001555 ).
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Anti-Inflamatórios não Esteroides , Combinação de Medicamentos , Cetoprofeno , Piridoxina , Tiamina , Trometamina , Vitamina B 12 , Humanos , Método Duplo-Cego , Tiamina/administração & dosagem , Tiamina/análogos & derivados , Tiamina/uso terapêutico , Cetoprofeno/administração & dosagem , Cetoprofeno/análogos & derivados , Feminino , Adulto , Piridoxina/administração & dosagem , Piridoxina/uso terapêutico , Masculino , Anti-Inflamatórios não Esteroides/administração & dosagem , Vitamina B 12/análogos & derivados , Vitamina B 12/administração & dosagem , Vitamina B 12/uso terapêutico , Pessoa de Meia-Idade , Trometamina/administração & dosagem , Estudos Prospectivos , Complexo Vitamínico B/administração & dosagem , Complexo Vitamínico B/uso terapêutico , Medição da Dor/métodos , Adulto JovemRESUMO
There is scarce evidence on sociodemographic and lifestyle characteristics that may explain adherence to different dietary patterns (DPs) during pregnancy. Our aims were to identify dietary patterns in a sample of pregnant Mexican women and to describe their association with selected sociodemographic and lifestyle characteristics. This is a secondary cross-sectional analysis of 252 mothers of children that participated as controls in a hospital-based case-control study of childhood leukemia. We obtained parents' information about selected sociodemographic characteristics, as well as alcohol and tobacco consumption. We also obtained dietary information during pregnancy. We identified DPs using cluster and factor analyses and we estimated their association with characteristics of interest. We identified two DPs using cluster analysis, which we called "Prudent" and "Non healthy", as well as three DPs through factor analysis, namely "Prudent", "Processed foods and fish", and "Chicken and vegetables". Characteristics associated with greater adherence to "Prudent" patterns were maternal education, older paternal age, not smoking, and being a government employee and/or uncovered population. Likewise, the "Processed foods and fish" pattern was associated with greater maternal and paternal education, as well as those with less household overcrowding. We did not identify sociodemographic variables related to the "Chicken and Vegetables" pattern. Our results may be useful to identify target populations that may benefit from interventions aimed to improve individual dietary decisions during pregnancy.
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Dieta , Estilo de Vida , Humanos , Feminino , México , Gravidez , Adulto , Estudos Transversais , Dieta/estatística & dados numéricos , Fatores Socioeconômicos , Comportamento Alimentar , Fatores Sociodemográficos , Estudos de Casos e Controles , Adulto Jovem , Fenômenos Fisiológicos da Nutrição Materna , Padrões DietéticosRESUMO
Cerebrovascular diseases in pediatric patients are relatively rare. Ischemic stroke in adolescents is associated with a poor prognosis. The most common causes include systemic diseases, such as heart disease and hypercoagulation disorders. It is important to mention that one of the most common acquired hypercoagulation states is the antiphospholipid syndrome (APS). Patients with this disease may present stroke as the first clinical manifestation, which not only increases morbidity in these patients but presents a diagnostic challenge. This case presents one example of how APS can present as a pediatric stroke. The diagnostic approach should always be through the presence of specific antibodies accompanied by the presence of a thromboembolic episode proven by catheterization or an imaging study. In the brain, the preferred imaging study is magnetic resonance imaging. Management is based on anticoagulation therapy and continuous monitoring in the intensive care unit.
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Crustose coralline algae (CCA) are a highly diverse group of habitat-forming, calcifying red macroalgae (Rhodophyta) with unique adaptations to diverse irradiance regimes. A distinctive CCA phenotype adaptation, which allows them to maximize photosynthetic performance in low light, is their content of a specific group of light-harvesting pigments called phycobilins. In this study, we assessed the potential of noninvasive hyperspectral imaging (HSI) in the visible spectrum (400-800 nm) to describe the phenotypic variability in phycobilin content of an Antarctic coralline, Tethysphytum antarcticum (Hapalidiales), from two distinct locations. We validated our measurements with pigment extractions and spectrophotometry analysis, in addition to DNA barcoding using the psbA marker. Targeted spectral indices were developed and correlated with phycobilin content using linear mixed models (R2 = 0.64-0.7). Once applied to the HSI, the models revealed the distinct phycoerythrin spatial distribution in the two site-specific CCA phenotypes, with thin and thick crusts, respectively. This study advances the capabilities of hyperspectral imaging as a tool to quantitatively study CCA pigmentation in relation to their phenotypic plasticity, which can be applied in laboratory studies and potentially in situ surveys using underwater hyperspectral imaging systems.
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Ficobilinas , Rodófitas , Regiões Antárticas , Ficobilinas/análise , Ficobilinas/metabolismo , Imageamento Hiperespectral/métodos , Pigmentos Biológicos/análise , Pigmentos Biológicos/metabolismo , Código de Barras de DNA TaxonômicoRESUMO
In vitro systems are useful tools for unravelling species differences in xenobiotic metabolism.The current work aimed to validate the technique of precision-cut liver slices (PCLS) for comparative studies on xenobiotic metabolism in swine and cattle.PCLS from swine (n = 3) and cattle (n = 3) were produced using a Brendel-VitronTM Tissue Slicer and cultured for 6 h. Tissue viability was preserved throughout the whole culture period.Metabolic viability was evaluated using the anthelmintics albendazole (ABZ) and fenbendazole (FBZ) as model drugs, as well as other substrates of hepatic monooxygenases: benzydamine (BZ) N-oxygenase (FMO-dependent), and the O-dealkylations of 7-ethoxyresorufin (EROD, CYP1A1-dependent) and 7-methoxyresorufin (MROD, CYP1A2-dependent).ABZ S-oxygenation resulted 6-fold (cattle) and 13.6-fold (swine) higher (p = 0.001) compared to FBZ S-oxygenation.Similar BZ N-oxygenation and EROD activities were observed in PCLS cultures from both species. MROD was 2.5-fold higher (p = 0.033) in swine than in cattle. Similarly, ABZ S-oxygenation was 1.7-fold higher (p = 0.0002) in swine than in cattle. Conversely, a 82% higher (p = 0.0003) rate of FBZ S-oxygenation was evidenced in PCLS cultures from cattle compared to those from swine.Overall, this work shows that PCLS cultures are useful to obtain relevant information on species differences in xenobiotic metabolism.
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Fígado , Xenobióticos , Animais , Bovinos , Xenobióticos/metabolismo , Fígado/metabolismo , SuínosRESUMO
The recent availability of open-access repositories of functional traits has revolutionized trait-based approaches in ecology and evolution. Nevertheless, the underrepresentation of tropical regions and lineages remains a pervasive bias in plant functional trait databases, which constrains large-scale assessments of plant ecology, evolution, and biogeography. Here, we present MelastomaTRAITs 1.0, a comprehensive and updatable database of functional traits for the pantropical Melastomataceae, the ninth-largest angiosperm family with 177 genera and more than 5800 species. Melastomataceae encompass species with a wide diversity of growth forms (herbs, shrubs, trees, epiphytes, and woody climbers), habitats (including tropical forests, savannas, grasslands, and wetlands from sea level to montane areas above the treeline), ecological strategies (from pioneer, edge-adapted and invasive species to shade-tolerant understory species), geographic distribution (from microendemic to continental-wide distribution), reproductive, pollination, and seed dispersal systems. MelastomaTRAITs builds on 581 references, such as taxonomic monographs, ecological research, and unpublished data, and includes four whole-plant traits, six leaf traits, 11 flower traits, 18 fruit traits, and 27 seed traits for 2520 species distributed in 144 genera across all 21 tribes. Most data come from the Neotropics where the family is most species-rich. Miconieae (the largest tribe) contains the highest number of trait records (49.6%) and species (41.1%) records. The trait types with the most information in the database were whole-plant traits, flowers, and leaf traits. With the breadth of functional traits recorded, our database helps to fill a gap in information for tropical plants and will significantly improve our capacity for large-scale trait-based syntheses across levels of organization, plant-animal interactions, regeneration ecology, and thereby support conservation and restoration programs. There are no copyright restrictions on the dataset; please cite this data paper when reusing the data.
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Bases de Dados Factuais , Melastomataceae , Ecossistema , Melastomataceae/fisiologia , Melastomataceae/genéticaRESUMO
PURPOSE: The present review will summarize FECD-associated genes and pathophysiology, diagnosis, current therapeutic approaches, and future treatment perspectives. METHODS: Literature review. RESULTS: Fuchs' endothelial corneal dystrophy (FECD) is the most common bilateral corneal dystrophy and accounts for one-third of all corneal transplants performed in the US. FECD is caused by a combination of genetic and non-heritable factors, and there are two types: early-onset FECD, which affects individuals from an early age and is usually more severe, and late-onset FECD, which is more common and typically manifests around the age of 40. The hallmark findings of FECD include progressive loss of corneal endothelial cells and the formation of focal excrescences (guttae) on the Descemet membrane. These pathophysiological changes result in progressive endothelial dysfunction, leading to a decrease in visual acuity and blindness in later stages. The present review will summarize FECD-associated genes and pathophysiology, diagnosis, current therapeutic approaches, and future treatment perspectives. CONCLUSION: With the characterization and understanding of FECD-related genes and ongoing research into regenerative therapies for corneal endothelium, we can hope to see more significant improvements in the future in the management and care of the disease.
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Transplante de Córnea , Distrofia Endotelial de Fuchs , Humanos , Distrofia Endotelial de Fuchs/diagnóstico , Distrofia Endotelial de Fuchs/genética , Distrofia Endotelial de Fuchs/terapia , Células Endoteliais , Endotélio Corneano , CegueiraRESUMO
Resumen La metahemoglobinemia ocasionalmente causa cianosis, particularmente cuando es congénita. Debido a sus vías enzimáticas deficientes y a la disminución de la capacidad de transporte de oxígeno, para los pacientes con metahemoglobinemia congénita es importante evitar la exposición a agentes oxidantes. A continuación, presentamos un paciente pediátrico con metahemoglobinemia congénita no diagnosticada preoperatoriamente que fue sometido a cateterismo con diagnóstico probable de hipertensión pulmonar bajo anestesia general. El paciente pediátrico era un niño de 10 años que presentaba una lectura de oximetría de pulso (SpO2) 92% antes de la inducción de la anestesia. La metahemoglobinemia se sospechó intraoperatoriamente por primera vez debido a un desajuste de la SpO2 de la oximetría de pulso digital y la SaO2 (saturación arterial de oxígeno), y luego se confirmó mediante múltiples longitudes de onda con la CO-oximetría. Se discuten la fisiopatología, etiología, manifestaciones clínicas, consideraciones anestésicas y opciones de tratamiento de la metahemoglobinemia.
Abstract Methemoglobinemia occasionally causes cyanosis particularly in congenital methemoglobinemia. Avoidance of exposure to oxidizing agents is important for patients with congenital methemoglobinemia because of their deficient enzymatic pathways and decreased oxygen-carrying capacity. Here, we present a pediatric patient with preoperatively undiagnosed congenital methemoglobinemia who underwent catheterization with probably diagnosis of pulmonar hypertension under general anesthesia. The pediatric patient was a 10-year-old who displayed a low pulse oximetry reading of 92% prior to induction of anesthesia. Methemoglobinemia was first suspected intraoperatively because of a mismatch of SpO2 of finger pulse oximetry and SaO2 of arterial blood, and was later confirmed by multiplewavelength CO-oximetry. The pathophysiology, etiology, clinical manifestations, anesthetic considerations, and treatment options of methemoglobinemia are discussed.
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Background: A heterogeneous geographic distribution of childhood acute lymphoblastic leukemia (ALL) cases has been described, possibly, related to the presence of different environmental factors. The aim of the present study was to explore the geographical distribution of childhood ALL cases in Greater Mexico City (GMC). Methods: A population-based case-control study was conducted. Children <18 years old, newly diagnosed with ALL and residents of GMC were included. Controls were patients without leukemia recruited from second-level public hospitals, frequency-matched by sex, age, and health institution with the cases. The residence address where the patients lived during the last year before diagnosis (cases) or the interview (controls) was used for geolocation. Kulldorff's spatial scan statistic was used to detect spatial clusters (SCs). Relative risks (RR), associated p-value and number of cases included for each cluster were obtained. Results: A total of 1054 cases with ALL were analyzed. Of these, 408 (38.7%) were distributed across eight SCs detected. A relative risk of 1.61 (p<0.0001) was observed for the main cluster. Similar results were noted for the remaining seven ones. Additionally, a proximity between SCs, electrical installations and petrochemical facilities was observed. Conclusions: The identification of SCs in certain regions of GMC suggest the possible role of environmental factors in the etiology of childhood ALL.
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Keywords: MRI, Imaging Sequences, Ultrasound, Mammography, CT, Angiography, Conventional Radiography Published under a CC BY 4.0 license. See also the commentary by Whitman and Vining in this issue.
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Mamografia , Radiologia , Radiografia , Prontuários Médicos , EscóciaRESUMO
Harnessing sunlight via photosensitizing molecules is key for novel optical applications and solar-to-chemical energy conversion. Exploiting abundant metals such as iron is attractive but becomes challenging due to typically fast nonradiative relaxation processes. In this work, we report on the luminescence and excited-state reactivity of the heteroleptic [FeIII(pzTp)(CN)3]- complex (pzTp = tetrakis(pyrazolyl)borate), which incorporates a σ-donating trispyrazolyl chelate ligand and three monodentate σ-donating and π-accepting cyanide ligands. Contrary to the nonemissive [Fe(CN)6]3-, a broad emission band centered at 600 nm at room temperature has been recorded for the heteroleptic analogue attributed to the radiative deactivation from a 2LMCT excited state with a luminescence quantum yield of 0.02% and a lifetime of 80 ps in chloroform at room temperature. Bimolecular reactivity of the 2LMCT excited state was successfully applied to different alcohol photo-oxidation, identifying a cyanide-H bonding as a key reaction intermediate. Finally, this research demonstrated the exciting potential of [Fe(pzTp)(CN)3]- as a photo-oxidant, paving the way for further exploration and development of emissive Fe-based photosensitizers competent for photochemical transformations.