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1.
Eur Radiol ; 2024 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-38244046

RESUMO

OBJECTIVE: To determine the inter-reader reliability and diagnostic performance of classification and severity scales of Neuropathy Score Reporting And Data System (NS-RADS) among readers of differing experience levels after limited teaching of the scoring system. METHODS: This is a multi-institutional, cross-sectional, retrospective study of MRI cases of proven peripheral neuropathy (PN) conditions. Thirty-two radiology readers with varying experience levels were recruited from different institutions. Each reader attended and received a structured presentation that described the NS-RADS classification system containing examples and reviewed published articles on this subject. The readers were then asked to perform NS-RADS scoring with recording of category, subcategory, and most likely diagnosis. Inter-reader agreements were evaluated by Conger's kappa and diagnostic accuracy was calculated for each reader as percent correct diagnosis. A linear mixed model was used to estimate and compare accuracy between trainees and attendings. RESULTS: Across all readers, agreement was good for NS-RADS category and moderate for subcategory. Inter-reader agreement of trainees was comparable to attendings (0.65 vs 0.65). Reader accuracy for attendings was 75% (95% CI 73%, 77%), slightly higher than for trainees (71% (69%, 72%), p = 0.0006) for nerves and comparable for muscles (attendings, 87.5% (95% CI 86.1-88.8%) and trainees, 86.6% (95% CI 85.2-87.9%), p = 0.4). NS-RADS accuracy was also higher than average accuracy for the most plausible diagnosis for attending radiologists at 67% (95% CI 63%, 71%) and for trainees at 65% (95% CI 60%, 69%) (p = 0.036). CONCLUSION: Non-expert radiologists interpreted PN conditions with good accuracy and moderate-to-good inter-reader reliability using the NS-RADS scoring system. CLINICAL RELEVANCE STATEMENT: The Neuropathy Score Reporting And Data System (NS-RADS) is an accurate and reliable MRI-based image scoring system for practical use for the diagnosis and grading of severity of peripheral neuromuscular disorders by both experienced and general radiologists. KEY POINTS: • The Neuropathy Score Reporting And Data System (NS-RADS) can be used effectively by non-expert radiologists to categorize peripheral neuropathy. • Across 32 different experience-level readers, the agreement was good for NS-RADS category and moderate for NS-RADS subcategory. • NS-RADS accuracy was higher than the average accuracy for the most plausible diagnosis for both attending radiologists and trainees (at 75%, 71% and 65%, 65%, respectively).

2.
JACS Au ; 3(12): 3473-3484, 2023 Dec 25.
Artigo em Inglês | MEDLINE | ID: mdl-38155638

RESUMO

Upcycling nonbiodegradable plastics such as polyolefins is paramount due to their ever-increasing demand and landfills after usage. Catalytic hydrogenolysis is highly appealing to convert polyolefins into targeted value-added products under mild reaction conditions compared with other methods, such as high-temperature incineration and pyrolysis. We have developed three isoreticular zirconium UiO-metal-organic frameworks (UiO-MOFs) node-supported ruthenium dihydrides (UiO-RuH2), which are efficient heterogeneous catalysts for hydrogenolysis of polyethylene at 200 °C, affording liquid hydrocarbons with a narrow distribution and excellent selectivity via shape-selective catalysis. UiO-66-RuH2 catalyzed hydrogenolysis of single-use low-density polyethylene (LDPE) produced a C12 centered narrow bell-shaped distribution of C8-C16 alkanes in >80% yield and 90% selectivity in the liquid phase. By tuning the pore sizes of the isoreticular UiO-RuH2 MOF catalysts, the distribution of the products could be systematically altered, affording different fuel-grade liquid hydrocarbons from LDPE in high yields. Our spectroscopic and theoretical studies and control experiments reveal that UiO-RuH2 catalysts enable highly efficient upcycling of plastic wastes under mild conditions owing to their unique combination of coordinatively unsaturated single-site Ru-active sites, uniform and tunable pores, well-defined porous structure, and superior stability. The kinetics and theoretical calculations also identify the C-C bond scission involving ß-alkyl transfer as the turnover-limiting step.

3.
J Am Chem Soc ; 145(41): 22845-22854, 2023 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-37815193

RESUMO

Valuable substituted phenols are accessible via the selective decarboxylation of hydroxybenzoic acid derivatives using multifunctional catalysts composed of bimetallic iron-ruthenium nanoparticles immobilized on an amine-functionalized supported ionic liquid phase (Fe25Ru75@SILP+IL-NEt2). The individual components of the catalytic system are assembled using a molecular approach to bring metal and amine sites into close contact on the support material, providing high stability and high decarboxylation activity. Operating under a hydrogen atmosphere was found to be essential to achieve high selectivity and yields. As the catalyst materials enable also the selective hydrogenation and hydrodeoxygenation of various additional functional groups (i.e., formyl, acyl, and nitro substituents), direct access to the corresponding phenols can be achieved via integrated tandem reactions. The approach opens versatile synthetic pathways for the production of valuable phenols from a wide range of readily available substrates, including compounds derived from lignocellulosic biomass.

4.
Adv Biol (Weinh) ; 7(8): e2300091, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-37403275

RESUMO

Ovarian cancer is the fifth leading cause of cancer-related deaths in women and the most lethal gynecologic cancer. It is curable when discovered at an early stage, but usually remains asymptomatic until advanced stages. It is crucial to diagnose the disease before it metastasizes to distant organs for optimal patient management. Conventional transvaginal ultrasound imaging offers limited sensitivity and specificity in the ovarian cancer detection. With molecularly targeted ligands addressing targets, such as kinase insert domain receptor (KDR), attached to contrast microbubbles, ultrasound molecular imaging (USMI) can be used to detect, characterize and monitor ovarian cancer at a molecular level. In this article, the authors propose a standardized protocol is proposed for the accurate correlation between in- vivo transvaginal KDR-targeted USMI and ex vivo histology and immunohistochemistry in clinical translational studies. The detailed procedures of in vivo USMI and ex vivo immunohistochemistry are described for four molecular markers, CD31 and KDR with a focus on how to enable the accurate correlation between in vivo imaging findings and ex vivo expression of the molecular markers, even if not the entire tumor could can be imaged by USMI, which is not an uncommon scenario in clinical translational studies. This work aims to enhance the workflow and the accuracy of characterization of ovarian masses on transvaginal USMI using histology and immunohistochemistry as reference standards, which involves sonographers, radiologists, surgeons, and pathologists in a highly collaborative research effort of USMI in cancer.


Assuntos
Imagem Molecular , Neoplasias Ovarianas , Feminino , Humanos , Imuno-Histoquímica , Ultrassonografia/métodos , Imagem Molecular/métodos , Microbolhas , Neoplasias Ovarianas/diagnóstico por imagem
5.
Dalton Trans ; 52(42): 15384-15393, 2023 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-37043211

RESUMO

N-Formylation of amines with CO2 as a cheap and non-toxic C1-feedstock and hydrosilane reducing agent is a practical and environment friendly method to synthesize formamides. This study describes an efficient and chemoselective mono-N-formylation of amines using CO2 and phenylsilane under mild conditions using a porous metal-organic framework (MOF)-supported single-site cobalt catalyst (pyrim-UiO-Co). The pyrim-UiO-Co MOF has a UiO-topology, and its organic linkers bear a pyridylimine ligated Co catalytic moiety. A wide range of aliphatic and aromatic amines are transformed into desired N-formamides in moderate to excellent yields under 1-5 bar CO2. Pyrim-UiO-Co is tolerant to various functional groups and could be recycled and reused at least 10 times. Mechanistic investigation using kinetic, spectroscopic and density functional theory studies suggests that the formylation of benzylamine proceeds sequentially via oxidative addition of PhSiH3 and CO2 insertion, followed by a turn-over limiting reaction with an amine. Our work highlights the importance of MOF-based Earth-abundant metal catalysts for the practical and eco-friendly synthesis of fine chemicals using cheap feedstocks.

6.
Eur Radiol ; 33(8): 5894-5906, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-36892645

RESUMO

OBJECTIVES: We aimed to develop and validate a deep learning system (DLS) by using an auxiliary section that extracts and outputs specific ultrasound diagnostic features to improve the explainable, clinical relevant utility of using DLS for detecting NAFLD. METHODS: In a community-based study of 4144 participants with abdominal ultrasound scan in Hangzhou, China, we sampled 928 (617 [66.5%] females, mean age: 56 years ± 13 [standard deviation]) participants (2 images per participant) to develop and validate DLS, a two-section neural network (2S-NNet). Radiologists' consensus diagnosis classified hepatic steatosis as none steatosis, mild, moderate, and severe. We also explored the NAFLD detection performance of six one-section neural network models and five fatty liver indices on our data set. We further evaluated the influence of participants' characteristics on the correctness of 2S-NNet by logistic regression. RESULTS: Area under the curve (AUROC) of 2S-NNet for hepatic steatosis was 0.90 for ≥ mild, 0.85 for ≥ moderate, and 0.93 for severe steatosis, and was 0.90 for NAFLD presence, 0.84 for moderate to severe NAFLD, and 0.93 for severe NAFLD. The AUROC of NAFLD severity was 0.88 for 2S-NNet, and 0.79-0.86 for one-section models. The AUROC of NAFLD presence was 0.90 for 2S-NNet, and 0.54-0.82 for fatty liver indices. Age, sex, body mass index, diabetes, fibrosis-4 index, android fat ratio, and skeletal muscle via dual-energy X-ray absorptiometry had no significant impact on the correctness of 2S-NNet (p > 0.05). CONCLUSIONS: By using two-section design, 2S-NNet had improved the performance for detecting NAFLD with more explainable, clinical relevant utility than using one-section design. KEY POINTS: • Based on the consensus review derived from radiologists, our DLS (2S-NNet) had an AUROC of 0.88 by using two-section design and yielded better performance for detecting NAFLD than using one-section design with more explainable, clinical relevant utility. • The 2S-NNet outperformed five fatty liver indices with the highest AUROCs (0.84-0.93 vs. 0.54-0.82) for different NAFLD severity screening, indicating screening utility of deep learning-based radiology may perform better than blood biomarker panels in epidemiology. • The correctness of 2S-NNet was not significantly influenced by individual's characteristics, including age, sex, body mass index, diabetes, fibrosis-4 index, android fat ratio, and skeletal muscle via dual-energy X-ray absorptiometry.


Assuntos
Aprendizado Profundo , Hepatopatia Gordurosa não Alcoólica , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , População do Leste Asiático , Fibrose , Fígado/diagnóstico por imagem , Hepatopatia Gordurosa não Alcoólica/diagnóstico por imagem , Hepatopatia Gordurosa não Alcoólica/epidemiologia , Ultrassonografia , Adulto , Idoso
7.
J Am Chem Soc ; 145(11): 6156-6165, 2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36897313

RESUMO

Acetic acid is an industrially important chemical, produced mainly via carbonylation of methanol using precious metal-based homogeneous catalysts. As a low-cost feedstock, methane is commercially transformed to acetic acid via a multistep process involving energy-intensive methane steam reforming, methanol synthesis, and, subsequently, methanol carbonylation. Here, we report a direct single-step conversion of methane to acetic acid using molecular oxygen (O2) as the oxidant under mild conditions over a mono-copper hydroxyl site confined in a porous cerium metal-organic framework (MOF), Ce-UiO-Cu(OH). The Ce-UiO MOF-supported single-site copper hydroxyl catalyst gave exceptionally high acetic acid productivity of 335 mmolgcat-1 in 96% selectivity with a Cu TON up to 400 at 115 °C in water. Our spectroscopic and theoretical studies and controlled experiments reveal that the conversion of methane to acetic acid occurs via oxidative carbonylation, where methane is first activated at the copper hydroxyl site via σ-bond metathesis to afford Cu-methyl species, followed by carbonylation with in situ-generated carbon monoxide and subsequent hydrolysis by water. This work may guide the rational design of heterogeneous abundant metal catalysts for the activation and conversion of methane to acetic acid and other valuable chemicals under mild and environmentally friendly reaction conditions.

8.
JAMA Netw Open ; 5(6): e2216370, 2022 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-35679042

RESUMO

Importance: The American College of Radiology (ACR) Ovarian-Adnexal Reporting and Data System (O-RADS) ultrasound (US) risk scoring system has been studied in a selected population of women referred for suspected or known adnexal lesions. This population has a higher frequency of malignant neoplasms than women presenting to radiology departments for pelvic ultrasonography for a variety of indications, potentially impacting the diagnostic performance of the risk scoring system. Objective: To evaluate the risk of malignant neoplasm and diagnostic performance of O-RADS US risk scoring system in a multi-institutional, nonselected cohort. Design, Setting, and Participants: This multi-institutional cohort study included a population of nonselected women in the United States who presented to radiology departments for routine pelvic ultrasonography between 2011 and 2014, with pathology confirmation imaging follow up or 2 years of clinical follow up. Exposure: Analysis of 1014 adnexal lesions using the O-RADS US risk stratification system. Main Outcomes and Measures: Frequency of ovarian cancer and diagnostic performance of the O-RADS US risk stratification system. Results: This study included 913 women with 1014 adnexal lesions. The mean (SD) age of the patients was 42.4 (13.9 years), and 674 of 913 (73.8%) were premenopausal. The overall frequency of malignant neoplasm was 8.4% (85 of 1014 adnexal lesions). The frequency of malignant neoplasm for O-RADS US 2 was 0.5% (3 of 657 lesions; <1% expected); O-RADS US 3, 4.5% (5 of 112 lesions; <10% expected); O-RADS US 4, 11.6% (18 of 155; 10%-50% expected); and O-RADS 5, 65.6% (59 of 90 lesions; >50% expected). O-RADS US 4 was the optimum cutoff for diagnosing cancer with sensitivity of 90.6% (95% CI, 82.3%-95.9%), specificity of 81.9% (95% CI, 79.3%-84.3%), positive predictive value of 31.4% (95% CI, 25.7%-37.7%) and negative predictive value of 99.0% (95% CI, 98.0%-99.6%). Conclusions and Relevance: In this cohort study of a nonselected patient population, the O-RADS US risk stratification system performed within the expected range as published by the ACR O-RADS US committee. The frequency of malignant neoplasm was at the lower end of the published range, partially because of the lower prevalence of cancer in a nonselected population. However, a high negative predictive value was maintained, and when a lesion can be classified as an O-RADS US 2, the risk of cancer is low, which is reassuring for both clinician and patient.


Assuntos
Neoplasias Ovarianas , Adulto , Estudos de Coortes , Feminino , Humanos , Neoplasias Ovarianas/diagnóstico por imagem , Neoplasias Ovarianas/epidemiologia , Neoplasias Ovarianas/patologia , Valor Preditivo dos Testes , Fatores de Risco , Ultrassonografia/métodos , Estados Unidos/epidemiologia
9.
Indian J Radiol Imaging ; 32(1): 81-112, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35722641

RESUMO

Pulmonary infections are the major cause of morbidity and mortality in immunocompromised patients and almost one-third of intensive care unit patients with pulmonary infections belong to the immunocompromised category. Multiple organisms may simultaneously infect an immunocompromised patient and the overwhelming burden of mixed infections further predisposes critically ill patients to acute hypoxemic respiratory failure. Notwithstanding that lung ultrasound is coming into vogue, the primary imaging investigation is a chest radiograph, followed by thoracic CT scan. This review based on our experience at tertiary care teaching hospitals provides insights into the spectrum of imaging features of various pulmonary infections occurring in immunocompromised patients. This review is unique as, firstly, the imaging spectrum described by us is categorized on basis of the etiological infective agent, comprehensively and emphatically correlated with the clinical setting of the patient. Secondly, a characteristic imaging pattern is emphasized in the clinical setting-imaging-pattern conglomerate, to highlight the most likely diagnosis possible in such a combination. Thirdly, the simulating conditions for a relevant differential diagnosis are discussed in each section. Fourthly, not only are the specific diagnostic and tissue sampling techniques for confirmation of the suspected etiological agent described, but the recommended pharmaco-therapeutic agents are also enumerated, so as to provide a more robust insight to the radiologist. Last but not the least, we summarize and conclude with a diagnostic algorithm, derived by us from the characteristic illustrative cases. The proposed algorithm, illustrated as a flowchart, emphasizes a diagnostic imaging approach comprising: correlation of the imaging pattern with clinical setting and with associated abnormalities in the thorax and in other organs/systems, which is comprehensively analyzed in arriving at the most likely diagnosis. Since a rapid evaluation and emergent management of such patients is of pressing concern not only to the radiologist, but also for the general physicians, pulmonologists, critical care specialists, oncologists and transplant surgery teams, we believe our review is very informative to a wide spectrum reader audience.

10.
Abdom Radiol (NY) ; 47(9): 3318-3326, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-35763052

RESUMO

PURPOSE: To evaluate interobserver agreement in assigning imaging features and classifying adnexal masses using the IOTA simple rules versus O-RADS lexicon and identify causes of discrepancy. METHODS: Pelvic ultrasound (US) examinations in 114 women with 118 adnexal masses were evaluated by eight radiologists blinded to the final diagnosis (4 attendings and 4 fellows) using IOTA simple rules and O-RADS lexicon. Each feature category was analyzed for interobserver agreement using intraclass correlation coefficient (ICC) for ordinal variables and free marginal kappa for nominal variables. The two-tailed significance level (a) was set at 0.05. RESULTS: For IOTA simple rules, interobserver agreement was almost perfect for three malignant lesion categories (M2-4) and substantial for the remaining two (M1, M5) with k-values of 0.80-0.82 and 0.68-0.69, respectively. Interobserver agreement was almost perfect for two benign feature categories (B2, B3), substantial for two (B4, B5) and moderate for one (B1) with k-values of 0.81-0.90, 0.69-0.70 and 0.60, respectively. For O-RADS, interobserver agreement was almost perfect for two out of ten feature categories (ascites and peritoneal nodules) with k-values of 0.89 and 0.97. Interobserver agreement ranged from fair to substantial for the remaining eight feature categories with k-values of 0.39-0.61. Fellows and attendings had ICC values of 0.725 and 0.517, respectively. CONCLUSION: O-RADS had variable interobserver agreement with overall good agreement. IOTA simple rules had more uniform interobserver agreement with overall excellent agreement. Greater reader experience did not improve interobserver agreement with O-RADS.


Assuntos
Doenças dos Anexos/diagnóstico por imagem , Neoplasias dos Genitais Femininos/diagnóstico por imagem , Variações Dependentes do Observador , Ascite/diagnóstico por imagem , Feminino , Humanos , Ultrassonografia/métodos
11.
Ultrasound Q ; 38(1): 72-82, 2022 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-35239631

RESUMO

ABSTRACT: Many uterine abnormalities present clinically with bleeding encompassing a broad spectrum of patients from postmenopausal spotting to life-threatening hemorrhage. Color and spectral Doppler imaging of the pelvis is often the first crucial investigation used to quickly establish the correct etiology of the uterine bleeding and guide clinical decision making and patient management.


Assuntos
Malformações Arteriovenosas , Feminino , Humanos , Pelve , Ultrassonografia Doppler em Cores/métodos , Hemorragia Uterina/etiologia , Útero/diagnóstico por imagem
12.
Radiology ; 303(3): 603-610, 2022 06.
Artigo em Inglês | MEDLINE | ID: mdl-35315722

RESUMO

Background Several US risk stratification schemas for assessing adnexal lesions exist. These multiple-subcategory systems may be more multifaceted than necessary for isolated adnexal lesions in average-risk women. Purpose To explore whether a US-based classification scheme of classic versus nonclassic appearance can be used to help appropriately triage women at average risk of ovarian cancer without compromising diagnostic performance. Materials and Methods This retrospective multicenter study included isolated ovarian lesions identified at pelvic US performed between January 2011 and June 2014, reviewed between September 2019 and September 2020. Lesions were considered isolated in the absence of ascites or peritoneal implants. Lesions were classified as classic or nonclassic based on sonographic appearance. Classic lesions included simple cysts, hemorrhagic cysts, endometriomas, and dermoids. Otherwise, lesions were considered nonclassic. Outcomes based on histopathologic results or clinical or imaging follow-up were recorded. Diagnostic performance and frequency of malignancy were calculated. Frequency of malignancy between age groups was compared using the χ2 test, and Poisson regression was used to explore relationships between imaging features and malignancy. Results A total of 970 isolated lesions in 878 women (mean age, 42 years ± 14 [SD]) were included. The malignancy rate for classic lesions was less than 1%. Of 970 lesions, 53 (6%) were malignant. The malignancy rate for nonclassic lesions was 32% (33 of 103) when blood flow was present and 8% (16 of 194) without blood flow (P < .001). For women older than 60 years, the malignancy rate was 50% (10 of 20 lesions) when blood flow was present and 13% (five of 38) without blood flow (P = .004). The sensitivity, specificity, positive predictive value, and negative predictive value of the classic-versus-nonclassic schema was 93% (49 of 53 lesions), 73% (669 of 917 lesions), 17% (49 of 297 lesions), and 99% (669 of 673 lesions), respectively, for detection of malignancy. Conclusion Using a US classification schema of classic- or nonclassic-appearing adnexal lesions resulted in high sensitivity and specificity in the diagnosis of malignancy in ovarian cancer. The highest risk of cancer was in isolated nonclassic lesions with blood flow in women older than 60 years. © RSNA, 2022 See also the editorial by Baumgarten in this issue.


Assuntos
Doenças dos Anexos , Cistos , Endometriose , Cistos Ovarianos , Neoplasias Ovarianas , Doenças dos Anexos/diagnóstico por imagem , Adulto , Carcinoma Epitelial do Ovário , Feminino , Humanos , Neoplasias Ovarianas/diagnóstico por imagem , Sensibilidade e Especificidade , Ultrassonografia/métodos
13.
Skeletal Radiol ; 51(9): 1865-1872, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35347408

RESUMO

OBJECTIVE: To introduce a 3D fast spin-echo (FSE) sequence technique that may replace conventional clinical 2D FSE sequences for examining the brachial plexus. MATERIALS AND METHODS: A 3D FSE sequence with motion-sensitized driven equilibrium magnitude preparation, triple-echo Dixon, and outer-volume suppression techniques, dubbed as MSDE-CUBE-fTED, was compared with clinical 2D T2-weighted and T1-weighted FSE sequences on the conventional brachial plexus exam of 14 volunteers. The resulting images were evaluated by two radiologists for fat suppression, blood flow suppression, nerve visualization, scalene muscle shape, surrounding fat planes, and diagnostic confidence. The inter-rater agreement of the reviewers was also measured. In addition, the signal magnitude ratios and contrast-to-noise ratios between nerve-to-vessel, nerve-to-muscle, and fat-to-muscle were compared. RESULTS: The MSDE-CUBE-fTED sequence scored significantly higher than the T2-weighed FSE sequence in all visualization categories (P < 0.05). Its score was not significantly different from that of the T1-weighted FSE in muscle and fat visualization (P ≥ 0.5). The inter-rater agreements were substantial (Gwet's agreement coefficient ≥ 0.7). The signal magnitude and contrast ratios were significantly higher in the MSDE-CUBE-fTED sequence (P < 0.05). CONCLUSION: Our results suggest that the MSDE-CUBE-fTED sequence can make a potential alternative to standard T2- and T1-weighted FSE sequences for examining the brachial plexus.


Assuntos
Plexo Braquial , Imageamento Tridimensional , Plexo Braquial/diagnóstico por imagem , Imagem de Difusão por Ressonância Magnética , Humanos , Imageamento Tridimensional/métodos , Imageamento por Ressonância Magnética/métodos , Movimento (Física)
14.
Inorg Chem ; 61(2): 1031-1040, 2022 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-34967211

RESUMO

The development of heterogeneous, chemoselective, and tandem catalytic systems using abundant metals is vital for the sustainable synthesis of fine and commodity chemicals. We report a robust and recyclable single-site cobalt-hydride catalyst based on a porous aluminum metal-organic framework (DUT-5 MOF) for chemoselective hydrogenation of arenes. The DUT-5 node-supported cobalt(II) hydride (DUT-5-CoH) is a versatile solid catalyst for chemoselective hydrogenation of a range of nonpolar and polar arenes, including heteroarenes such as pyridines, quinolines, isoquinolines, indoles, and furans to afford cycloalkanes and saturated heterocycles in excellent yields. DUT-5-CoH exhibited excellent functional group tolerance and could be reusable at least five times without decreased activity. The same MOF-Co catalyst was also efficient for tandem hydrogenation-hydrodeoxygenation of aryl carbonyl compounds, including biomass-derived platform molecules such as furfural and hydroxymethylfurfural to cycloalkanes. In the case of hydrogenation of cumene, our spectroscopic, kinetic, and density functional theory (DFT) studies suggest the insertion of a trisubstituted alkene intermediate into the Co-H bond occurring in the turnover limiting step. Our work highlights the potential of MOF-supported single-site base-metal catalysts for sustainable and environment-friendly industrial production of chemicals and biofuels.

15.
Semin Musculoskelet Radiol ; 25(4): 546-557, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-34706384

RESUMO

One of the key principles in the interpretation of radiology images is the ability to differentiate between normal and abnormal findings. This article provides a comprehensive overview of normal structures and anatomical variants occurring around the elbow including potential diagnostic pitfalls. We discuss frequently observed anatomical variants found in routine clinical practice associated with osseous, ligamentous, musculotendinous, and neurovascular structures at the elbow that may simulate pathology or predispose to symptoms under specific circumstances.


Assuntos
Articulação do Cotovelo , Cotovelo , Cotovelo/diagnóstico por imagem , Articulação do Cotovelo/diagnóstico por imagem , Humanos , Ligamentos , Imageamento por Ressonância Magnética
16.
Inorg Chem ; 60(12): 9029-9039, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-34085831

RESUMO

Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal-organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H2. The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl2 followed by the reaction of NaEt3BH. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of CoII and AlIII centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt-hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.

17.
Angew Chem Int Ed Engl ; 60(19): 10964-10970, 2021 05 03.
Artigo em Inglês | MEDLINE | ID: mdl-33539670

RESUMO

We report a strategy to develop heterogeneous single-site enantioselective catalysts based on naturally occurring amino acids and earth-abundant metals for eco-friendly asymmetric catalysis. The grafting of amino acids within the pores of a metal-organic framework (MOF), followed by post-synthetic metalation with iron precursor, affords highly active and enantioselective (>99 % ee for 10 examples) catalysts for hydrosilylation and hydroboration of carbonyl compounds. Impressively, the MOF-Fe catalyst displayed high turnover numbers of up to 10 000 and was recycled and reused more than 15 times without diminishing the enantioselectivity. MOF-Fe displayed much higher activity and enantioselectivity than its homogeneous control catalyst, likely due to the formation of robust single-site catalyst in the MOF through site-isolation.

18.
Eur Radiol ; 31(6): 3555-3563, 2021 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-33236205

RESUMO

OBJECTIVES: Most of the shoulder magnetic resonance imaging (MRI) examination focuses on internal joint structures but disregarding other structures like the distal brachial plexus, which may miss important findings. Hereby, we attempt to evaluate the prevalence of distal brachial plexus abnormalities and/or muscular denervation changes seen on routine shoulder MRI examinations and discuss common pathologies affecting the distal brachial plexus. MATERIAL AND METHODS: A total of 701 routine shoulder MRI studies were evaluated. The evaluation of each exam was focused on the visualized brachial plexus elements and musculature abnormalities in each case. If any abnormalities of plexus and/or musculature were found, potential underlying etiologies such as paralabral or spinoglenoid notch cysts, infiltrative/primary masses on imaging, history of prior viral illness, and radiation therapy were searched. It was then confirmed whether the abnormal findings were mentioned in the exam reports or not. RESULTS: Thirty-four cases (4.85%) demonstrated abnormal findings of the visualized brachial plexus cords or branches and/or musculature. It was observed that in 35.3% of exam reports these findings were not mentioned, mainly missing subtle nerve abnormalities, but correctly reporting and interpreting the encountered muscle abnormalities. CONCLUSION: The distal brachial plexus and its branches should be included in the search pattern for shoulder MRI examinations. KEY POINTS: • Normal T2 signal of the brachial plexus is iso- to slightly hyperintense to muscle but less signal intense than fluid. • Diffuse, geographic muscle edema is an indirect sign of brachial plexus pathology. • Increased T2-weighted nerve signal with or without caliber or course change should be reported and followed up to find the underlying etiology.


Assuntos
Neuropatias do Plexo Braquial , Plexo Braquial , Plexo Braquial/diagnóstico por imagem , Neuropatias do Plexo Braquial/diagnóstico por imagem , Neuropatias do Plexo Braquial/epidemiologia , Humanos , Imageamento por Ressonância Magnética , Prevalência , Ombro/diagnóstico por imagem
19.
Inorg Chem ; 59(15): 10473-10481, 2020 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-32649190

RESUMO

We report a highly active single-site heterogeneous cobalt-catalyst based on a porous and robust pyridylimine-functionalized metal-organic frameworks (pyrim-MOF) for chemoselective borylation of arene and benzylic C-H bonds. The pyrim-MOF having UiO-68 topology, constructed from zirconium-cluster secondary building units and pyridylimine-functionalized dicarboxylate bridging linkers, was metalated with CoCl2 followed by treatment of NaEt3BH to give the cobalt-functionalized MOF-catalyst (pyrim-MOF-Co). Pyrim-MOF-Co has a broad substrate scope, allowing the C-H borylation of halogen-, alkoxy-, alkyl-substituted arenes as well as heterocyclic ring systems using B2pin2 or HBpin (pin = pinacolate) as the borylating agent to afford the corresponding arene- or alkyl-boronate esters in good yields. Pyrim-MOF-Co gave a turnover number (TON) of up to 2500 and could be recycled and reused at least 9 times. Pyrim-MOF-Co was also significantly more robust and active than its homogeneous control, highlighting the beneficial effect of active-site isolation within the MOF framework that prevents intermolecular decomposition. The experimental and computational studies suggested (pyrim•-)CoI(THF) as the active catalytic species within the MOF, which undergoes a mechanistic pathway of oxidative addition, turnover limiting σ-bond metathesis, followed by reductive elimination to afford the boronate ester.

20.
Indian J Radiol Imaging ; 30(1): 32-45, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32476748

RESUMO

Infertility is a major social and clinical problem affecting 13-15% of couples worldwide. The pelvic causes of female infertility are categorized as ovarian disorders, tubal, peritubal disorders, and uterine disorders. Appropriate selection of an imaging modality is essential to accurately diagnose the aetiology of infertlity, since the imaging diagnosis directs the appropriate treatment to be instituted. Imaging evaluation begins with hystero- salpingography (HSG), to evaluate fallopian tube patency. Uterine filling defects and contour abnormalities may be discovered at HSG but usually require further characterization with pelvic ultrasound (US), sono-hysterography (syn: hystero-sonography/saline infusion sonography) or pelvic magnetic resonance imaging (MRI), when US remains inconclusive. The major limitation of hysterographic US, is its inability to visualize extraluminal pathologies, which are better evaluated by pelvic US and MRI. Although pelvic US is a valuable modality in diagnosing entities comprising the garden variety, however, extensive pelvic inflammatory disease, complex tubo-ovarian pathologies, deep-seated endometriosis deposits with its related complications, Mulllerian duct anomalies, uterine synechiae and adenomyosis, often remain unresolved by both transabdominal and transvaginal US. Thus, MRI comes to the rescue and has a niche role in resolving complex adnexal masses, endometriosis, and Mullerian duct anomalies with greater ease. This is a review, based on the authors' experience at tertiary care teaching hospitals and aims to provide an imaging approach towards the abnormalities which are not definitively diagnosed by ultrasound alone.

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