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1.
Nature ; 613(7942): 71-76, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36600065

RESUMO

The two natural allotropes of carbon, diamond and graphite, are extended networks of sp3-hybridized and sp2-hybridized atoms, respectively1. By mixing different hybridizations and geometries of carbon, one could conceptually construct countless synthetic allotropes. Here we introduce graphullerene, a two-dimensional crystalline polymer of C60 that bridges the gulf between molecular and extended carbon materials. Its constituent fullerene subunits arrange hexagonally in a covalently interconnected molecular sheet. We report charge-neutral, purely carbon-based macroscopic crystals that are large enough to be mechanically exfoliated to produce molecularly thin flakes with clean interfaces-a critical requirement for the creation of heterostructures and optoelectronic devices2. The synthesis entails growing single crystals of layered polymeric (Mg4C60)∞ by chemical vapour transport and subsequently removing the magnesium with dilute acid. We explore the thermal conductivity of this material and find it to be much higher than that of molecular C60, which is a consequence of the in-plane covalent bonding. Furthermore, imaging few-layer graphullerene flakes using transmission electron microscopy and near-field nano-photoluminescence spectroscopy reveals the existence of moiré-like superlattices3. More broadly, the synthesis of extended carbon structures by polymerization of molecular precursors charts a clear path to the systematic design of materials for the construction of two-dimensional heterostructures with tunable optoelectronic properties.

2.
Nano Lett ; 23(22): 10449-10457, 2023 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-37934894

RESUMO

Two-dimensional antiferromagnets have garnered considerable interest for the next generation of functional spintronics. However, many bulk materials from which two-dimensional antiferromagnets are isolated are limited by their air sensitivity, low ordering temperatures, and insulating transport properties. TaFe1+yTe3 aims to address these challenges with increased air stability, metallic transport, and robust antiferromagnetism. Here, we synthesize TaFe1+yTe3 (y = 0.14), identify its structural, magnetic, and electronic properties, and elucidate the relationships between them. Axial-dependent high-field magnetization measurements on TaFe1.14Te3 reveal saturation magnetic fields ranging between 27 and 30 T with saturation magnetic moments of 2.05-2.12 µB. Magnetotransport measurements confirm that TaFe1.14Te3 is metallic with strong coupling between magnetic order and electronic transport. Angle-resolved photoemission spectroscopy measurements across the magnetic transition uncover a complex interplay between itinerant electrons and local magnetic moments that drives the magnetic transition. We demonstrate the ability to isolate few-layer sheets of TaFe1.14Te3, establishing TaFe1.14Te3 as a potential platform for two-dimensional spintronics.

3.
Nat Mater ; 21(7): 754-760, 2022 07.
Artigo em Inglês | MEDLINE | ID: mdl-35513502

RESUMO

Semiconductors, featuring tunable electrical transport, and magnets, featuring tunable spin configurations, form the basis of many information technologies. A long-standing challenge has been to realize materials that integrate and connect these two distinct properties. Two-dimensional (2D) materials offer a platform to realize this concept, but known 2D magnetic semiconductors are electrically insulating in their magnetic phase. Here we demonstrate tunable electron transport within the magnetic phase of the 2D semiconductor CrSBr and reveal strong coupling between its magnetic order and charge transport. This provides an opportunity to characterize the layer-dependent magnetic order of CrSBr down to the monolayer via magnetotransport. Exploiting the sensitivity of magnetoresistance to magnetic order, we uncover a second regime characterized by coupling between charge carriers and magnetic defects. The magnetoresistance within this regime can be dynamically and reversibly tuned by varying the carrier concentration using an electrostatic gate, providing a mechanism for controlling charge transport in 2D magnets.


Assuntos
Magnetismo , Semicondutores , Fenômenos Magnéticos , Imãs
4.
J Chem Phys ; 158(16)2023 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-37093146

RESUMO

Quasi-2D nanomaterials such as semiconducting nanoplatelets (NPLs) have drawn considerable interest due to their tunable optical properties and large surface to volume ratios. Cadmium selenide (CdSe) NPLs are of particular fundamental interest since their thicknesses can be controlled with atomic precision using well-established solution-phase synthetic techniques. Additionally, their large surface area makes them especially susceptible to changes in the identity of the capping ligands and, therefore, good model systems for understanding surface chemistry. In the current work, we explore the role of these ligands in altering the lattice parameters and optical properties of CdSe NPLs. We build on prior research that has employed varying binding groups, including thiols, phosphonic acids, and halides, to demonstrate ligand-dependent optical bandgap changes and concomitant lattice distortions as determined by powder x-ray diffraction (PXRD). Our work investigates the correlations between ligand-induced optical and structural changes with a series of ligands that maintain a consistent carboxylic acid binding group, thus allowing us to probe secondary ligand effects. We perform ligand exchanges on oleic acid-capped CdSe NPLs with benzoic acids, cinnamic acids, and cyclohexanecarboxylic acid. In all cases, the optical bandgap decreases upon ligand exchange, and a correlated expansion in the thickness of the NPLs is observed via PXRD. We also observe that the benzoic acids produce larger optical and structural distortions than the cinnamic acids. We show that the optical and structural correlation is nearly quantitatively described by quantum confinement effects, with the thicker quantum wells exhibiting smaller energy gaps.

5.
J Am Chem Soc ; 144(12): 5263-5267, 2022 03 30.
Artigo em Inglês | MEDLINE | ID: mdl-35302759

RESUMO

The amplification of chiral absorbance and emission is a primary figure of merit for the design of chiral chromophores. However, for dyes to be practically relevant in chiroptical applications, they must also absorb and/or emit chiral light over broad wavelength ranges. We investigate the interplay between molecular symmetry and broad-band chiral absorbance in a series of [6]helicenes. We find that an asymmetric [6]helicene containing two distinct chromophores absorbs chiral light across a much wider wavelength range than the symmetric [6]helicenes investigated here. Chemically reducing the helicenes shifts the absorption edge of the ECD spectra into the near-infrared wavelength range while preserving broad chiral absorption, producing a [6]helicene that absorbs a single handedness of light across the entire visible wavelength range.


Assuntos
Corantes , Luz , Corantes/química
6.
J Am Chem Soc ; 144(1): 74-79, 2022 01 12.
Artigo em Inglês | MEDLINE | ID: mdl-34978439

RESUMO

Coating two-dimensional (2D) materials with molecules bearing tunable properties imparts their surfaces with functionalities for applications in sensing, nanoelectronics, nanofabrication, and electrochemistry. Here, we report a method for the site-selective surface functionalization of 2D superatomic Re6Se8Cl2 monolayers. First, we activate bulk layered Re6Se8Cl2 by intercalating lithium and then exfoliate the intercalation compound Li2Re6Se8Cl2 in N-methylformamide (NMF). Heating the resulting solution eliminates LiCl to produce monolayer Re6Se8(NMF)2-x (x ≈ 0.4) as high-quality nanosheets. The unpaired electrons on each cluster in Re6Se8(NMF)2-x enable covalent surface functionalization through radical-based chemistry. We demonstrate this to produce four previously unknown surface-functionalized 2D superatomic materials: Re6Se8I2, Re6Se8(SPh)2, Re6Se8(SPhNH2)2, and Re6Se8(SC16H33)2. Transmission electron microscopy, chemical analysis, and vibrational spectroscopy reveal that the in-plane structure of the 2D Re6Se8 material is preserved through surface functionalization. We find that the incoming groups control the density of vacancy defects and the solubility of the 2D material. This approach will find utility in installing a broad array of chemical functionalities on the surface of 2D superatomic materials as a means to systematically tune their physical properties, chemical reactivity, and solution processability.

7.
J Am Chem Soc ; 144(1): 306-313, 2022 01 12.
Artigo em Inglês | MEDLINE | ID: mdl-34937334

RESUMO

We show that reaction pathways from a single superatom motif can be controlled through subtle electronic modification of the outer ligand spheres. Chevrel-type [Co6Se8L6] (L = PR3, CO) superatoms are used to form carbene-terminated clusters, the reactivity of which can be influenced through the electronic effects of the surrounding ligands. This carbene provides new routes for ligand substitution chemistry, which is used to selectively install cyanide or pyridine ligands which were previously inaccessible in these cobalt-based clusters. The surrounding ligands also impact the ability of this carbene to create larger fused clusters of the type [Co12Se16L10], providing underlying information for cluster fusion mechanisms. We use this information to develop methods of creating dimeric clusters with functionalized surface ligands with site specificity, putting new ligands in specific positions on this anisotropic core. Finally, adjusting the carbene intermediates can also be used to perturb the geometry of the [Co6Se8] core itself, as we demonstrate with a multicarbene adduct that displays a substantially anisotropic core. These additional levels of synthetic control could prove instrumental for using superatomic clusters for many applications including catalysis, electronic devices, and creating novel extended structures.

8.
Phys Chem Chem Phys ; 24(18): 11206-11212, 2022 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-35481469

RESUMO

Hydrate formation is often unavoidable during crystallization, leading to performance degradation of pharmaceuticals and energetics. In some cases, water molecules trapped within crystal lattices can be substituted for hydrogen peroxide, improving the solubility of drugs and detonation performance of explosives. The present work compares hydrates and hydrogen peroxide solvates in two ways: (1) analyzing structural motifs present in crystal structures accessed from the Cambridge Structural Database and (2) developing potential energy surfaces for water and hydrogen peroxide interacting with functional groups of interest at geometries relevant to the solid state. By elucidating fundamental differences in local interactions that can be formed with molecules of hydrogen peroxide and/or water, the analyses presented here provide a foundation for the design and selection of candidate molecules for the formation of hydrogen peroxide solvates.


Assuntos
Peróxido de Hidrogênio , Água , Cristalização , Peróxido de Hidrogênio/química , Solubilidade , Água/química
9.
BMC Med Imaging ; 22(1): 176, 2022 10 07.
Artigo em Inglês | MEDLINE | ID: mdl-36207686

RESUMO

BACKGROUND: We aimed to evaluate the value of using preoperative magnetic resonance imaging (MRI) features and clinical indicators to predict the early response of hepatocellular carcinoma (HCC) to transcatheter arterial chemoembolization (TACE). We also aimed to establish a preoperative prediction model. METHODS: We retrospectively reviewed data of 111 patients with HCC who underwent magnetic resonance imaging (MRI) before the first TACE and underwent MRI or computed tomography between 30 and 60 days after TACE. We used the modified response evaluation criteria in solid tumors for evaluating the TACE response. We used univariate and multivariate logistic regression analyses to identify independent predictors based on MRI features and clinical indicators. Moreover, receiver operating characteristic (ROC) curve analyses were performed to assess the diagnostic performance of the prediction model and each independent predictor. RESULTS: Among the 111 included patients, 85 were men (76.6%). Patient age was 31-86 years (average age, 61.08 ± 11.50 years). After the first treatment session, 56/111 (50.5%) patients showed an objective response (complete response + partial response), whereas the remaining showed non-response (stable disease + local progressive disease). In the univariate analysis, we identified irregular margins, number of nodules, and satellite nodules as predictors of early objective response. However, in the multivariate logistic regression analysis, irregular margins, number of nodules and pretreatment platelet were identified as the independent predictors of early objective response. A combined prediction model was then established, which factored in irregular margins, the number of nodules, and the pretreatment platelet count. This model showed good diagnostic performance (area under the ROC curve = 0.755), with the sensitivity, specificity, positive predictive value, and negative predictive value being 78.6%, 69.1%, 72.1%, and 76.0%, respectively. CONCLUSIONS: Irregular margins, the number of nodules and the pretreatment platelet count are independent predictors of the early response of HCC to TACE. Our clinical combined model can provide a superior predictive power to a single indicator.


Assuntos
Carcinoma Hepatocelular , Quimioembolização Terapêutica , Neoplasias Hepáticas , Adulto , Idoso , Idoso de 80 Anos ou mais , Carcinoma Hepatocelular/diagnóstico por imagem , Carcinoma Hepatocelular/patologia , Carcinoma Hepatocelular/terapia , Quimioembolização Terapêutica/métodos , Feminino , Humanos , Neoplasias Hepáticas/diagnóstico por imagem , Neoplasias Hepáticas/patologia , Neoplasias Hepáticas/terapia , Imageamento por Ressonância Magnética/métodos , Masculino , Pessoa de Meia-Idade , Estudos Retrospectivos , Resultado do Tratamento
10.
Nano Lett ; 21(8): 3511-3517, 2021 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-33856213

RESUMO

The advent of two-dimensional (2D) magnets offers unprecedented control over electrons and spins. A key factor in determining exchange coupling and magnetic order is symmetry. Here, we apply second harmonic generation (SHG) to probe a 2D magnetic semiconductor CrSBr. We find that monolayers are ferromagnetically ordered below 146 K, an observation enabled by the discovery of a large magnetic dipole SHG effect in the centrosymmetric structure. In multilayers, the ferromagnetic monolayers are coupled antiferromagnetically, and in contrast to other 2D magnets, the Néel temperature of CrSBr increases with decreasing layer number. We identify magnetic dipole and magnetic toroidal moments as order parameters of the ferromagnetic monolayer and antiferromagnetic bilayer, respectively. These findings establish CrSBr as an exciting 2D magnetic semiconductor and extend the SHG probe of magnetic symmetry to the monolayer limit, opening the door to exploring the applications of magnetic-electronic coupling and the magnetic toroidal moment.

11.
J Am Chem Soc ; 143(1): 109-113, 2021 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-33356207

RESUMO

Layered van der Waals (vdW) materials belonging to the MM'Te4 structure class have recently received intense attention due to their ability to host exotic electronic transport phenomena, such as in-plane transport anisotropy, Weyl nodes, and superconductivity. Here we report two new vdW materials with strongly anisotropic in-plane structures featuring stripes of metallic TaTe2 and semiconducting FeTe2, α-TaFeTe4 and ß-TaFeTe4. We find that the structure of α-TaFeTe4 produces strongly anisotropic in-plane electronic transport (anisotropy ratio of up to 250%), outcompeting all other vdW metals, and demonstrate that it can be mechanically exfoliated to the two-dimensional (2D) limit. We also explore the possibility that broken inversion symmetry in ß-TaFeTe4 produces Weyl points in the electronic band structure. Eight Weyl nodes slightly below the Fermi energy are computationally identified for ß-TaFeTe4, indicating they may contribute to the transport behavior of this polytype. These findings identify the TaFeTe4 polytypes as an ideal platform for investigation of 2D transport anisotropy and chiral charge transport as a result of broken symmetry.

12.
J Am Chem Soc ; 143(2): 983-991, 2021 01 20.
Artigo em Inglês | MEDLINE | ID: mdl-33377771

RESUMO

Here we report the synthesis of two polyhelicene frameworks consisting, from end-to-end, of 18 and 24 fused benzene rings. The latter exhibits the largest electronic circular dichroism in the visible spectrum of any molecule. These shape-persistent helical nanoribbons incorporate multiple helicenes, a class of contorted polycyclic aromatic molecules consisting of ortho-annulated rings. These conjugated, chiral molecules have interesting chemical, biological, and chiroptical properties; however, there are very few helicenes with extraordinary chiroptical response over a broad range of the visible spectrum-a key criterion for applications such as chiral optoelectronics. In this report, we show that coupling the polyhelicene framework with multiple perylene-diimide subunits elicits a significant chiroptic response. Notably, the molar circular dichroism increases faster than the absorptivity of these molecules as their helical axis lengthens. Computational analysis reveals that the greatly amplified circular dichroism arises from exciton-like interactions between the perylene-diimide and the helicene moieties. We predict that even greater chiroptic enhancement will result from further axial elongation of these nanoribbons, which can be readily enabled via the iterative synthetic method presented herein.


Assuntos
Nanoestruturas/química , Compostos Policíclicos/química , Teoria da Densidade Funcional , Estrutura Molecular , Compostos Policíclicos/síntese química , Estereoisomerismo
13.
J Magn Reson Imaging ; 54(6): 1922-1934, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-33963801

RESUMO

BACKGROUND: The Liver Imaging Reporting and Data System (LI-RADS) was established for noninvasive diagnosis for hepatocellular carcinoma (HCC). However, whether training can improve readers' agreement with the expert consensus and inter-reader agreement for final categories is still unclear. PURPOSE: To explore training effectiveness on readers' agreement with the expert consensus and inter-reader agreement. STUDY TYPE: Prospective. SUBJECTS: Seventy lesions in 61 patients at risk of HCC undergoing liver MRI; 20 visiting scholars. FIELD STRENGTH/SEQUENCE: 1.5 T or 3 T, Dual-echo T1 WI, Fast spin-echo T2 WI, SE-EPI DWI, and Dynamic multiphase fast gradient-echo T1 WI. ASSESSMENT: Seventy lesions assigned LI-RADS categories of LR1-LR5, LR-M, and LR-TIV by three radiologists in consensus were randomly selected, with 10 cases for each category. The consensus opinion was the standard reference. The third radiologist delivered the training. Twenty readers reviewed images independently and assigned each an LI-RADS category both before and after the training. STATISTICAL TESTS: Accuracy, sensitivity, specificity, positive predictive value, negative predictive value, positive likelihood ratio, negative likelihood ratio, receiver operating characteristic (ROC) analysis, simple and weighted kappa statistics, and Fleiss kappa statistics. RESULTS: Before and after training: readers' AUC (areas under ROC) for LR-1-LR-5, LR-M, and LR-TIV were 0.898 vs. 0.913, 0.711 vs. 0.876, 0.747 vs. 0.860, 0.724 vs. 0.815, 0.844 vs. 0.895, 0.688 vs. 0.873, and 0.720 vs. 0.948, respectively, and all improved significantly (P < 0.05), except LR-1(P = 0.25). Inter-reader agreement between readers for LR-1-LR-5, LR-M, LR-TIV were 0.725 vs. 0.751, 0.325 vs. 0.607, 0.330 vs. 0.559, 0.284 vs. 0.488, 0.447 vs. 0.648, 0.229 vs. 0.589, and 0.362 vs. 0.852, respectively, and all increased significantly (P < 0.05). For training effectiveness on both AUC and inter-reader agreement, LR-TIV, LR-M, and LR-2 improved most, and LR-1 made the least. DATA CONCLUSION: This study shows LI-RADS training could improve reader agreement with the expert consensus and inter-reader agreement for final categories. LEVEL OF EVIDENCE: 2 TECHNICAL EFFICACY STAGE: 2.


Assuntos
Carcinoma Hepatocelular , Neoplasias Hepáticas , Carcinoma Hepatocelular/diagnóstico por imagem , Consenso , Meios de Contraste , Humanos , Neoplasias Hepáticas/diagnóstico por imagem , Imageamento por Ressonância Magnética , Estudos Prospectivos , Estudos Retrospectivos , Sensibilidade e Especificidade
14.
Artigo em Inglês | MEDLINE | ID: mdl-34054285

RESUMO

Cancer is among the leading cause of death around the world, causing close to 10 million deaths each year. Significant efforts have been devoted to developing novel technologies that can detect and treat cancer early and effectively to reduce cancer recurrences, treatment costs, and mortality. Gold nanoparticles (GNP) have been given particular attention for its use with photo-induced hyperthermia coupled with novel immunotherapy methods to provide a new platform for highly selective and less invasive cancer treatment. Among the various GNP platforms, gold nanostars (GNS) have a unique star-shaped geometric structure that allows superior light absorption and photothermal heating. This photothermal effect have also been found to amplify the anti-tumor immune response and can be exploited with adjuvant treatments using immune checkpoint inhibitors. This combination treatment known as Synergistic Immuno Photo Nanotherapy (SYMPHONY) has been shown to reverse tumor-mediated immunosuppression and has led to effective and long-lasting immunity against not only primary tumors but also cancer metastasis. This overview highlights the development and applications of GNS-mediated therapy developed in our laboratory for cancer treatment. This paper also presents recent results of experimental studies to illustrate the superior performance of GNS for photothermal treatment applications.

15.
Appl Opt ; 60(3): 720-726, 2021 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-33690454

RESUMO

Our current work exploits direct laser writing (DLW) and low one-photon absorption (LOPA) in a low-cost three-dimensional optical fabrication system designed to print micrometric polymeric structures. Micropedestals were obtained by focusing a laser beam on a photoresist layer deposited on a silica glass substrate. Subsequent coating with rhodamine 6G dye allows these pedestals to function as microlasers upon optical excitation at 532 nm. Our microlasers, with a diameter of ∼53µm and a height of ∼40µm, exhibit a broad fluorescence peak in the spectral range 540-600 nm, in addition to narrow lasing peaks, exhibiting quality factors Q exceeding 2000 and a lasing threshold of ∼5µJcm-2. The observed free spectral range associated with the lasing peaks of ∼1.3nm is consistent with simulations, which we include in this paper. In addition, we present simulations for the longitudinal shift of the patterning laser spot, which occurs particularly for relatively thick photoresist layers, coupled with a large index contrast at the photoresist top surface. Such a shift could introduce errors in the resulting microfabricated structures if left unaccounted for. We hope that our work will contribute to the development of microlasers for various photonic applications, particularly if dimensions can be reduced, for on-chip optical communications and data processing.

16.
Anal Bioanal Chem ; 412(14): 3457-3466, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32147769

RESUMO

Molecular biomarkers such as microRNAs (miRNAs) play important roles in regulating various developmental processes in plants. Understanding these pathways will help bioengineer designing organisms for efficient biomass accumulation. Current methods for RNA analysis require sample extraction and multi-step sample analysis, hindering work in field studies. Recent work in the incorporation of nanomaterials for plant bioengineering research is leading the way of an agri-tech revolution. As an example, surface-enhanced Raman scattering (SERS)-based sensors can be used to monitor RNA in vivo. However, the use of SERS in the field has been limited due to issues with observing Raman signal over complex background. To this end, shifted-excitation Raman difference spectroscopy (SERDS) offers an effective solution to extract the SERS signal from high background based on a physical approach. In this manuscript, we report the first application of SERDS on SERS sensors. We investigated this technique on SERS sensor developed for the detection of a microRNA biomarker, miR858. We tested the technique on in vitro samples and validated the technique by detecting the presence of exogenous miR858 in plants directly under ambient light in a growth chamber. The possibility of moving the detection of nucleic acid targets outside the constraints of laboratory setting enables numerous important bioengineering applications. Such applications can revolutionize biofuel production and agri-tech through the use of nanotechnology-based monitoring of plant growth, plant health, and exposure to pollution and pathogens.


Assuntos
MicroRNAs/análise , Plantas/química , RNA de Plantas/análise , Análise Espectral Raman/instrumentação , Técnicas Biossensoriais/instrumentação , Desenho de Equipamento , Propriedades de Superfície
17.
Clin Radiol ; 75(6): 478.e25-478.e35, 2020 06.
Artigo em Inglês | MEDLINE | ID: mdl-32089261

RESUMO

AIM: To investigate the diagnostic performance of Liver Imaging Reporting and Data System (LI-RADS) version 2017 for diagnosing hepatocellular carcinoma (HCC), by using major features only and combined major and ancillary features on computed tomography (CT). MATERIALS AND METHODS: A total of 147 HCC, 35 non-HCC malignancy, and 37 benign lesions in 205 patients at high risk of HCC were evaluated retrospectively, and the diagnostic performance of LI-RADS for diagnosing HCC were compared between using major features only and adopting major and ancillary features in combination. RESULTS: When using LR-5 as a predictor for diagnosing HCC, the diagnostic specificity (90.3% versus 91.7%), positive predictive value (92.3% versus 93.3%), and accuracy (68% versus 68.8%) were increased based on major and ancillary features in combination than just using major features on CT. When using LR-4/5 as a predictor for diagnosing HCC, the diagnostic sensitivity (78.9% versus 85.7%), negative predictive value (64.4% versus 72%), and accuracy (78.5% versus 82.2%) were increased while preserving a high specificity (77.8% versus 75%), according to major and ancillary features in combination rather than just using major features on CT. The LI-RADS categories of 8.7% (19/219) lesions were adjusted by adding the ancillary features on CT. CONCLUSION: Adding the ancillary features visible on CT can improve the diagnostic performance of the LI-RADS v2017 algorithm for diagnosing HCC, especially for LR-3 lesions.


Assuntos
Algoritmos , Carcinoma Hepatocelular/diagnóstico por imagem , Neoplasias Hepáticas/diagnóstico por imagem , Tomografia Computadorizada por Raios X/métodos , Adulto , Idoso , Idoso de 80 Anos ou mais , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Sistemas de Informação em Radiologia , Estudos Retrospectivos , Sensibilidade e Especificidade
18.
Artigo em Zh | MEDLINE | ID: mdl-32131151

RESUMO

Objective: To investigate the mental health of clinical first-line medical staff in COVID-19 epidemic and provide theoretical basis for psychological intervention. Methods: The mental health status of the first-line medical staff was investigated by Self-rating Anxiety Scale(SAS) and Post-Traumatic Stress Disorder Self- rating Scale (PTSD-SS). From February 7 to 14, 2020, 246 medical staff participated in the treatment of COVID-19 were investigated using cluster sampling, and received 230 responses, with a recovery rate of 93.5%. Results: The incidence of anxiety in medical staff was 23.04% (53/230) , and the score of SAS was(42.91±10.89). Among them, the incidence of severe anxiety, moderate anxiety and mild anxiety were 2.17%(5/230) , 4.78%(11/230) and 16.09%(37/230) , respectively. The incidence of anxiety in female medical staff was higher than that in male [25.67%(48/187) vs 11.63%(5/43) , Z=-2.008, P=0.045], the score of SAS in female medical staff was higher than that in male [(43.78±11.12) vs (39.14±9.01) , t=-2.548, P=0.012]. The incidence of anxiety in nurses was higher than that in doctors[26.88% (43/160) vs 14.29% (10/70) , Z=-2.066, P=0.039], and the score of SAS in nurses was higher than that in doctors [ (44.84±10.42) vs (38.50±10.72) , t=-4.207, P<0.001]. The incidence of stress disorder in medical staff was 27.39% (63/230) , and the score of PTSD-SS was (42.92±17.88) . The score of PTSD-SS in female medical staff was higher than that in male[ (44.30±18.42) vs (36.91±13.95) , t=-2.472, P=0.014]. Conclusion: In COVID-19 epidemic , the incidence of anxiety and stress disorder is high among medical staff. Medical institutions should strengthen the training of psychological skills of medical staff. Special attention should be paid to the mental health of female nurses.


Assuntos
Ansiedade/epidemiologia , Infecções por Coronavirus/epidemiologia , Infecções por Coronavirus/terapia , Epidemias , Corpo Clínico Hospitalar/psicologia , Pneumonia Viral/epidemiologia , Pneumonia Viral/terapia , Transtornos de Estresse Pós-Traumáticos/epidemiologia , COVID-19 , China/epidemiologia , Feminino , Inquéritos Epidemiológicos , Humanos , Incidência , Masculino , Corpo Clínico Hospitalar/estatística & dados numéricos , Pandemias , Escalas de Graduação Psiquiátrica , Centros de Atenção Terciária
19.
J Am Chem Soc ; 141(46): 18551-18559, 2019 11 20.
Artigo em Inglês | MEDLINE | ID: mdl-31692339

RESUMO

Selective access to a targeted isomer is often critical in the synthesis of biologically active molecules. Whereas small-molecule reagents and catalysts often act with anticipated site- and stereoselectivity, this predictability does not extend to enzymes. Further, the lack of access to catalysts that provide complementary selectivity creates a challenge in the application of biocatalysis in synthesis. Here, we report an approach for accessing biocatalysts with complementary selectivity that is orthogonal to protein engineering. Through the use of a sequence similarity network (SSN), a number of sequences were selected, and the corresponding biocatalysts were evaluated for reactivity and selectivity. With a number of biocatalysts identified that operate with complementary site- and stereoselectivity, these catalysts were employed in the stereodivergent, chemoenzymatic synthesis of azaphilone natural products. Specifically, the first syntheses of trichoflectin, deflectin-1a, and lunatoic acid A were achieved. In addition, chemoenzymatic syntheses of these azaphilones supplied enantioenriched material for reassignment of the absolute configuration of trichoflectin and deflectin-1a based on optical rotation, CD spectra, and X-ray crystallography.


Assuntos
Benzopiranos/síntese química , Produtos Biológicos/síntese química , Pigmentos Biológicos/síntese química , Benzopiranos/química , Biocatálise , Produtos Biológicos/química , Pigmentos Biológicos/química , Estereoisomerismo
20.
Anal Chem ; 91(5): 3319-3326, 2019 03 05.
Artigo em Inglês | MEDLINE | ID: mdl-30676724

RESUMO

Surface-enhanced Raman spectroscopy (SERS) is a powerful analytical spectroscopy offering advantages ranging from "vibrational fingerprints" to multiplexed detection. However, the use of this technique in real-world applications has been limited due to difficulties in detecting inherently weak Raman signals often embedded in strong interfering background signals. A variety of plasmonics-active platforms have been developed to increase Raman signals but are not sufficient to extract weak SERS signals from intense interfering background signals. Herein, we describe a practical method, referred to as polarization modulation-SERS (PM-SERS), which utilizes the polarization dependence of anisotropic SERS-active nanostructures to modulate the plasmonic effect to extract SERS signals and remove background. The modulation is obtained by switching the polarization of the excitation source at a specific frequency involving addition of only few optical components such as liquid crystal polarizers to a typical Raman setup. In this work, we characterized the polarization-dependent response of the SERS substrates fabricated using the oblique angle evaporation (OAV) technique and their response under laser excitation using a polarization modulated source. We demonstrated that the PM-SERS method can extract the analyte weak SERS signals from the strong interfering background signal in different situations, involving a fluorescent sample and a strong background light, and we show the possibility of using PM-SERS at a quasi-real time rate (0.5 Hz). We believe that the PM-SERS method will help expand the translation of applications that utilize SERS-substrates to real-world settings.

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