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BACKGROUND AND AIMS: Metabolic dysfunction-associated steatotic liver disease (MASLD) encompasses a broad and continuous spectrum of liver diseases ranging from fatty liver to steatohepatitis. The intricate interactions of genetic, epigenetic, and environmental factors in the development and progression of MASLD remain elusive. Here, we aimed to achieve an integrative understanding of the genomic and transcriptomic alterations throughout the progression of MASLD. APPROACH AND RESULTS: RNA-Seq profiling (n = 146) and whole-exome sequencing (n = 132) of MASLD liver tissue samples identified 3 transcriptomic subtypes (G1-G3) of MASLD, which were characterized by stepwise pathological and molecular progression of the disease. Macrophage-driven inflammatory activities were identified as a key feature for differentiating these subtypes. This subtype-discriminating macrophage interplay was significantly associated with both the expression and genetic variation of the dsDNA sensor IFI16 (rs6940, A>T, T779S), establishing it as a fundamental molecular factor in MASLD progression. The in vitro dsDNA-IFI16 binding experiments and structural modeling revealed that the IFI16 variant exhibited increased stability and stronger dsDNA binding affinity compared to the wild-type. Further downstream investigation suggested that the IFI16 variant exacerbated DNA sensing-mediated inflammatory signals through mitochondrial dysfunction-related signaling of the IFI16-PYCARD-CASP1 pathway. CONCLUSIONS: This study unveils a comprehensive understanding of MASLD progression through transcriptomic classification, highlighting the crucial roles of IFI16 variants. Targeting the IFI16-PYCARD-CASP1 pathway may pave the way for the development of novel diagnostics and therapeutics for MASLD.
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BACKGROUND/AIMS: Metabolic dysfunction-associated steatotic liver disease (MASLD) is characterized by fat accumulation in the liver. MASLD encompasses both steatosis and MASH. Since MASH can lead to cirrhosis and liver cancer, steatosis and MASH must be distinguished during patient treatment. Here, we investigate the genomes, epigenomes, and transcriptomes of MASLD patients to identify signature gene set for more accurate tracking of MASLD progression. METHODS: Biopsy-tissue and blood samples from patients with 134 MASLD, comprising 60 steatosis and 74 MASH patients were performed omics analysis. SVM learning algorithm were used to calculate most predictive features. Linear regression was applied to find signature gene set that distinguish the stage of MASLD and to validate their application into independent cohort of MASLD. RESULTS: After performing WGS, WES, WGBS, and total RNA-seq on 134 biopsy samples from confirmed MASLD patients, we provided 1,955 MASLD-associated features, out of 3,176 somatic variant callings, 58 DMRs, and 1,393 DEGs that track MASLD progression. Then, we used a SVM learning algorithm to analyze the data and select the most predictive features. Using linear regression, we identified a signature gene set capable of differentiating the various stages of MASLD and verified it in different independent cohorts of MASLD and a liver cancer cohort. CONCLUSION: We identified a signature gene set (i.e., CAPG, HYAL3, WIPI1, TREM2, SPP1, and RNASE6) with strong potential as a panel of diagnostic genes of MASLD-associated disease.
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Hígado Graso , Neoplasias Hepáticas , Humanos , Algoritmos , Neoplasias Hepáticas/diagnóstico , Neoplasias Hepáticas/genética , Progresión de la EnfermedadRESUMEN
For optimizing steady-state performance in organic electrochemical transistors (OECTs), both molecular design and structural alignment approaches must work in tandem to minimize energetic and microstructural disorders in polymeric mixed ionic-electronic conductor films. Herein, a series of poly(diketopyrrolopyrrole)s bearing various lengths of aliphatic-glycol hybrid side chains (PDPP-mEG; m = 2-5) is developed to achieve high-performance p-type OECTs. PDPP-4EG polymer with the optimized length of side chains exhibits excellent crystallinity owing to enhanced lamellar and backbone interactions. Furthermore, the improved structural ordering in PDPP-4EG films significantly decreases trap state density and energetic disorder. Consequently, PDPP-4EG-based OECT devices produce a mobility-volumetric capacitance product ([µC*]) of 702 F V-1 cm-1 s-1 and a hole mobility of 6.49 ± 0.60 cm2 V-1 s-1 . Finally, for achieving the optimal structural ordering along the OECT channel direction, a floating film transfer method is employed to reinforce the unidirectional orientation of polymer chains, leading to a substantially increased figure-of-merit [µC*] to over 800 F V-1 cm-1 s-1 . The research demonstrates the importance of side chain engineering of polymeric mixed ionic-electronic conductors in conjunction with their anisotropic microstructural optimization to maximize OECT characteristics.
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With the rapid development of human-friendly wearable devices, energy storage components are required to have skin-like stretchability or free-form to fit closer and more comfortably to the human body. This study introduces a hierarchically interpenetrated reentrant microcellular structure combined with 2D cellular graphene/MXene/carbon nanotubes (CNTs) and 3D cellular melamine foam. This composite structure works as a stretchable framework of lithium metal composite electrodes to provide stretchability for lithium metal electrodes, which are promising as next-generation energy storage systems. The interpenetrated but independent cellular structures successfully obtain stable structural deformability from the nonconductive and deformable melamine foam, while at the same time, high electrical conductivity, lithiophilicity, and mechanical stability of the graphene/CNT/MXene network serve as a lithium deposition support during the electrodeposition of lithium. The reentrant structure is fabricated by radial compressing the hierarchical cellular structures to take advantage of the structural stretchability of the accordion-like reentrant frameworks. The lithium-deposited composite electrodes exhibit much lower overpotential during Li stripping and plating than lithium metal foil anodes and show stable electrochemical performances under 30% of mechanical strain. The reentrant microcellular electrodes offer great potential for advanced designs of lithium metal electrodes for stretchable batteries with high energy density.
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Biofuel cells (BFCs) based on enzymatic electrodes hold great promise as power sources for biomedical devices. However, their practical use is hindered by low electron transfer efficiency and poor operational stability of enzymatic electrodes. Here, a novel mediator-free multi-ply BFC that overcomes these limitations and exhibits both substantially high-power output and long-term operational stability is presented. The approach involves the utilization of interfacial interaction-induced assembly between hydrophilic glucose oxidase (GOx) and hydrophobic conductive indium tin oxide nanoparticles (ITO NPs) with distinctive shapes, along with a multi-ply electrode system. For the preparation of the anode, GOx and oleylamine-stabilized ITO NPs with bipod/tripod type are covalently assembled onto the host fiber electrode composed of multi-walled carbon nanotubes and gold (Au) NPs. Remarkably, despite the contrasting hydrophilic and hydrophobic properties, this interfacial assembly approach allows for the formation of nanoblended GOx/ITO NP film, enabling efficient electron transfer within the anode. Additionally, the cathode is prepared by sputtering Pt onto the host electrode. Furthermore, the multi-ply fiber electrode system exhibits unprecedented high-power output (≈10.4 mW cm-2 ) and excellent operational stability (2.1 mW cm-2 , ≈49% after 60 days of continuous operation). The approach can provide a basis for the development of high-performance BFCs.
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The effective spatial distribution and arrangement of electrochemically active and conductive components within metal oxide nanoparticle (MO NP)-based electrodes significantly impact their energy storage performance. Unfortunately, conventional electrode preparation processes have much difficulty addressing this issue. Herein, this work demonstrates that a unique nanoblending assembly based on favorable and direct interfacial interactions between high-energy MO NPs and interface-modified carbon nanoclusters (CNs) notably enhances the capacities and charge transfer kinetics of binder-free electrodes in lithium-ion batteries (LIBs). For this study, carboxylic acid (COOH)-functionalized carbon nanoclusters (CCNs) are consecutively assembled with bulky ligand-stabilized MO NPs through ligand-exchange-induced multidentate binding between the COOH groups of CCNs and the surface of NPs. This nanoblending assembly homogeneously distributes conductive CCNs within densely packed MO NP arrays without insulating organics (i.e., polymeric binders and/or ligands) and prevents the aggregation/segregation of electrode components, thus markedly reducing contact resistance between neighboring NPs. Furthermore, when these CCN-mediated MO NP electrodes are formed on highly porous fibril-type current collectors (FCCs) for LIB electrodes, they deliver outstanding areal performance, which can be further improved through simple multistacking. The findings provide a basis for better understanding the relationship between interfacial interaction/structures and charge transfer processes and for developing high-performance energy storage electrodes.
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Recent advances in fabricating stretchable and transparent electrodes have led to various techniques for establishing next-generation form-factor optoelectronic devices. Wavy Ag nanowire networks with large curvature radii are promising platforms as stretchable and transparent electrodes due to their high electrical conductivity and stretchability even at very high transparency. However, there are disadvantages such as intrinsic nonregular conductivity, large surface roughness, and nanowire oxidation in air. Here, we introduce electrically synergistic but mechanically independent composite electrodes by sequentially introducing conducting polymers and ionic liquids into the wavy Ag nanowire network to maintain the superior performance of the stretchable transparent electrode while ensuring overall conductivity, lower roughness, and long-term stability. In particular, plenty of ionic liquids can be incorporated into the uniformly coated conducting polymer so that the elastic modulus can be significantly lowered and sliding can occur at the nanowire interface, thereby obtaining the high mechanical stretchability of the composite electrode. Finally, as a result of applying the composite film as the stretchable transparent electrode of stretchable organic solar cells, the organic solar cell exhibits a high power conversion efficiency of 11.3% and 89% compared to the initial efficiency even at 20% tensile strain, demonstrating excellent stretching stability.
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PURPOSE: The purpose of this study was to determine the feasibility of early Superb microvascular imaging (SMI) for prediction of the effect of HCC treatment after transcatheter arterial chemoembolization (TACE). MATERIALS AND METHODS: A total of 96 HCCs (70 patients) treated with TACE between September 2021 and May 2022 were included in this study. SMI, Color Doppler imaging (CDI), and Power Doppler imaging (PDI) were performed the day after TACE for evaluation of intratumoral vascularity of the lesion using an Aplio500 ultrasound scanner (Toshiba Medical Systems, Corporation, Tochigi, Japan). Grading of the vascular presence was performed using a five-point scale. A dynamic CT image taken after 29-42 days was used for comparison of sensitivity, specificity, and accuracy for detection of tumor vascularity between SMI, CDI, and PDI. Univariate and multivariate analysis were performed for assessment of factors affecting intratumoral vascularity. RESULTS: Fifty-eight lesions (60%) showed complete remission (CR) and 38 lesions (40%) showed partial response (PR) or no response at 29-42 days on Multi-detector Computed Tomography (MDCT) after TACE. SMI showed sensitivity of 86.84% for detection of intratumoral flow, which was significantly higher compared with that of CDI (10.53%, p < 0.001) and PDI (36.84%, p < 0.001). The results of multivariate analysis indicated that tumor size was a significant factor in detection of blood flow using the SMI technique. CONCLUSION: Early SMI may be utilized as an adjunctive diagnostic test for evaluation of treated lesions after TACE, particularly when the location of the tumor is in an area of the liver where a suitable sonic window can be identified.
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Carcinoma Hepatocelular , Quimioembolización Terapéutica , Neoplasias Hepáticas , Humanos , Carcinoma Hepatocelular/diagnóstico por imagen , Carcinoma Hepatocelular/terapia , Neoplasias Hepáticas/diagnóstico por imagen , Neoplasias Hepáticas/terapia , Neoplasias Hepáticas/irrigación sanguínea , Estudios de Factibilidad , Sensibilidad y Especificidad , Quimioembolización Terapéutica/métodosRESUMEN
Ciliated foregut cyst is a relatively rare disease; thus, most reports are in the form of case studies. This benign cyst is usually found in the mediastinum and account for approximately 20% of all mediastinal masses. However, it is rarely found in the hepatobiliary and peripancreatic regions. Approximately 20 cases of ciliated foregut cysts involving the pancreas have been reported in the Enlgish literature. Here, we present a case of ciliated foregut cyst that occurred in the tail of the pancreas in a 29-year-old female. The patient's ultrasonography, CT, and MRI findings are presented, along with a review of the literature.
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Supramolecular assembly based on aromatic interactions can provide well-defined nanostructures with an understanding of intermolecular interactions at the molecular level. The peptide assembly via a supramolecular approach can overcome the inherent limitations of bioactive peptides, such as proteolytic degradations and rapid internalizations into the cytosol. Although extensive research has been carried out on supramolecular peptide materials with a two-dimensional (2D) structure, more needs to be reported on biological activity studies using well-defined 2D peptide materials. Physical and chemical properties of the 2D peptide assembly attributed to their large surface area and flexibility can show low cytotoxicity, enhanced molecular loading, and higher bioconjugation efficiency in biological applications. Here, we report supramolecular 2D materials based on the pyrene-grafted amphiphilic peptide, which contains a peptide sequence (Asp-Gly-Glu-Ala; DGEA) that is reported to bind to the integrin α2ß1 receptor in 2D cell membranes. The addition of octafluoronaphthalene (OFN) to the pyrene-grafted peptide could induce a well-ordered 2D assembly by face-centered arene-perfluoroarene stacking. The DGEA-peptide 2D assembly with a flat structure, structural stability against enzymatic degradations, and a larger size can enhance the proliferation and differentiation of muscle cells via continuous interactions with cell membrane receptors integrin α2ß1 showing a low intracellular uptake (15%) compared to that (62%) of the vesicular peptide assembly. These supramolecular approaches via the arene-perfluoroarene interaction provide a strategy to fabricate well-defined 2D peptide materials with an understanding of assembly at the molecular level for the next-generation peptide materials.
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Integrina alfa2beta1 , Péptidos , Péptidos/química , Mioblastos , Diferenciación Celular , Proliferación CelularRESUMEN
The growth of lithium (Li) dendrites reduces the lifespan of Li-metal batteries and causes safety issues. Herein, hierarchically porous aramid nanofiber separators capable of effectively suppressing the Li dendrite growth while maintaining highly stable cycle performances at high charge/discharge rates are reported. A two-step solvent exchange process combined with reprotonation-mediated self-assembly is utilized to control the bimodal porous structure of the separators. In particular, when ethanol and water are used sequentially, aramid nanofibers form hierarchical porous structures containing nanopores in macroporous polymer frameworks to yield a mechanically robust membrane with high porosity of 97% or more. The optimized samples exhibit high ionic conductivities of 1.87-4.04 mS cm-1 and high Li-ion transference numbers of 0.77-0.84 because of the ultrahigh porosity and selective affinity to anions. Li-metal symmetric cells do not show any noticeable presence of dendrites after 100 cycles, and they operate stably for more than 1500 cycles even under extreme conditions with a high current density of >20 mA cm-2 . In addition, the LiFePO4 /Li full cell retains 86.3% of its capacity after 1000 cycles at a charge rate of 30 C.
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Hydrogels have diverse chemical properties and can exhibit reversibly large mechanical deformations in response to external stimuli; these characteristics suggest that hydrogels are promising materials for soft robots. However, reported actuators based on hydrogels generally suffer from slow response speed and/or poor controllability due to intrinsic material limitations and electrode fabrication technologies. Here, we report a hydrogel actuator that operates at low voltages (<3 volts) with high performance (strain > 50%, energy density > 7 × 105 joules per cubic meter, and power density > 3 × 104 watts per cubic meter), surpassing existing hydrogel actuators and other types of electroactive soft actuators. The enhanced performance of our actuator is due to the formation of wrinkled nanomembrane electrodes that exhibit high conductivity and excellent mechanical deformation through capillary-assisted assembly of metal nanoparticles and deswelling-induced wrinkled structures. By applying an electric potential through the wrinkled nanomembrane electrodes that sandwich the hydrogel, we were able to trigger a reversible and substantial electroosmotic water flow inside a hydrogel film, which drove the controlled swelling of the hydrogel. The high energy efficiency and power density of our wrinkled nanomembrane electrode-induced actuator enabled the fabrication of an untethered insect-scale aquabot integrated with an on-board control unit demonstrating maneuverability with fast locomotion speed (1.02 body length per second), which occupies only 2% of the total mass of the robot.
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Hidrogeles , Agua , Animales , Hidrogeles/química , Electrodos , Conductividad Eléctrica , InsectosRESUMEN
Effective incorporation of conductive and energy storage materials into 3D porous textiles plays a pivotal role in developing and designing high-performance energy storage devices. Here, a fibril-type textile pseudocapacitor electrode with outstanding capacity, good rate capability, and excellent mechanical stability through controlled interfacial interaction-induced electroplating is reported. First, tetraoctylammonium bromide-stabilized copper sulfide nanoparticles (TOABr-CuS NPs) are uniformly assembled onto cotton textiles. This approach converts insulating textiles to conductive textiles preserving their intrinsically porous structure with an extremely large surface area. For the preparation of textile current collector with bulk metal-like electrical conductivity, Ni is additionally electroplated onto the CuS NP-assembled textiles (i.e., Ni-EPT). Furthermore, a pseudocapacitive NiCo-layered double hydroxide (LDH) layer is subsequently electroplated onto Ni-EPT for the cathode. The formed NiCo-LDH electroplated textiles (i.e., NiCo-EPT) exhibit a high areal capacitance of 12.2 F cm-2 (at 10 mA cm-2 ), good rate performance, and excellent cycling stability. Particularly, the areal capacity of NiCo-EPT can be further increased through their subsequent stacking. The 3-stack NiCo-EPT delivers an unprecedentedly high areal capacitance of 28.8 F cm-2 (at 30 mA cm-2 ), which outperforms those of textile-based pseudocapacitor electrodes reported to date.
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Galvanoplastia , Nanopartículas , Electrodos , TextilesRESUMEN
Ionogels are emerging materials for advanced electrochemical devices; however, their mechanical instability to external stresses has raised concerns about their safety. This study reports aligned bacterial nanocellulose (BC) ionogel films swelled with the model ionic liquid (IL) of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) for an unprecedented combination of high stiffness and high energy dissipation without significant loss of ionic conductivity. The aligned BC ionogel films are prepared through wet-state stretching methods, followed by drying and swelling by ILs. The aligned ionogel films exhibit significantly improved dynamic mechanical properties, overcoming the mechanical conventional limit of traditional materials by 2.0 times at 25 °C and by a maximum of 4.0 times at 0 °C. Additionally, the same samples exhibit relatively high ionic conductivities of 0.16 mS cm-1 at 20 °C and 0.45 mS cm-1 at 60 °C with storage moduli over 10 GPa. The synergistic effect of the mechanical reinforcements by alignment of the BC nanofibers and the plasticizing effects by ILs could be attributed to the significant enhancement of dynamic mechanical properties and the retention of ionic conductivities. These results will lead to a deeper understanding of the material design for mechanically superior ionogel systems with increasing demands for advanced electronic and electrochemical devices.
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Lithium-sulfur (Li-S) batteries are promising as next-generation energy storage systems. Adsorbents for sulfide species are favorably applied to the cathode, but this substrate often results in a surface-passivating lithium sulfide(Li2 S) film with a strong adsorption of Li2 S. Here, an amorphous titanium suboxide (a-TiOx) is presented that strongly adsorbs lithium polysulfides (Li2 Sx , x < 6) but relatively weakly adsorbs to Li2 S. With these characteristics, the a-TiOx achieves high conversion of Li2 Sx and high sulfur utilization accompanying the growth of particulate Li2 S. The DFT calculations present a mechanism for particulate growth driven by the promoted diffusion and favorable clustering of Li2 S. The a-TiOx -coated carbon nanotube-assembled film (CNTF) cathode substrate cell achieves a high discharge capacity equivalent to 90% sulfur utilization at 0.2 C. The cell also delivers a high capacity of 850 mAh g-1 even at the ultra-high-speed of 10 C and also exhibits high stability of capacity loss of 0.0226% per cycle up to 500 cycles. The a-TiOx /CNTF is stacked to achieve a high loading of 7.5 mg S cm-2 , achieving a practical areal capacity of 10.1 mAh cm-2 .
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N-Acetylneuraminic acid (Neu5Ac), one of the abundant types of sialic acid, is an emerging anticancer agent owing to its ability to target selectins in the plasma membrane of cancer cells. Considering the functionality of Neu5Ac, obtaining novel Neu5Ac-conjugated materials with a selective and an enhanced antitumor activity has remained a challenge. Herein, we report the supramolecular materials of three novel amphiphiles composed of Neu5Ac as a hydrophilic segment and pyrene or adamantane as a hydrophobic segment. The synthetic amphiphiles 1, 2, and 3 self-assembled into ribbons, vesicles, and irregular aggregates in an aqueous solution, respectively. Among the materials, vesicles of amphiphile 2 showed the most substantial selectivity toward cancer cells, followed by cell death due to the production of reactive oxygen species by the pyrene group. The dual advantage of Neu5Ac-selectivity and the pyrene-cytotoxicity of vesicles of amphiphile 2 can provide a strategy for effective anticancer materials.
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Ácido N-Acetilneuramínico , Membrana Celular/metabolismo , Interacciones Hidrofóbicas e Hidrofílicas , Ácido N-Acetilneuramínico/metabolismoRESUMEN
For next-generation wearable and implantable devices, energy storage devices should be soft and mechanically deformable and easily printable on any substrate or active devices. Herein, we introduce a fully stretchable lithium-ion battery system for free-form configurations in which all components, including electrodes, current collectors, separators, and encapsulants, are intrinsically stretchable and printable. The stretchable electrode acquires intrinsic stretchability and improved interfacial adhesion with the active materials via a functionalized physically cross-linked organogel as a stretchable binder and separator. Intrinsically stretchable current collectors are fabricated in the form of nanocomposites consisting of a matrix with excellent barrier properties without swelling in organic electrolytes and nanostructure-controlled multimodal conductive fillers. Due to structural and materials freedoms, we successfully fabricate several types of stretchable lithium-ion battery that reliably operates under various stretch deformations with capacity and rate capability comparable with a nonstretchable battery over 2.5 mWh cm-2 at 0.5 C, even under high mass loading conditions over 10 mg cm-2, including stacked configuration, direct integration on both sides of a stretch fabric, and application of various electrode materials and electrolytes. Especially, our stretchable battery printed on a stretch fabric also exhibits high performance and stretch/long-term stabilities in the air even with wearing and pulling.
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OBJECTIVE: To characterize the use of portal venous or delayed phase CT as an alternative to estimate washout for the non-invasive diagnosis of hepatocellular carcinoma (HCC) on gadoxetic acid-enhanced MRI in combination with other features. METHODS: This retrospective study included 226 observations (n = 162 patients) at high risk for HCC imaged with gadoxetic acid-enhanced MRI and enhanced liver CT between March 2015 and March 2018. Two radiologists independently evaluated two sets of images and assigned the final Liver Imaging Reporting and Data System (LI-RADS) categories by consensus using gadoxetic acid-enhanced MRI. LR-1, LR-2, LR-5, and LR-M were excluded from the study.The observations were divided using different criteria for washout: hypointensity on the portal venous phase (PVP) at MRI (criteria 1), hypointensity on PVP at MRI and/or hypoattenuation on the PVP/delayed phase at dynamic CT (criteria 2), and hypointensity on the PVP and/or hepatobiliary phase at MRI (criteria 3). The sensitivity, specificity, and accuracy for the diagnosis of HCC were analyzed for each criterion. RESULTS: Using gadoxetic acid-enhanced, 226 lesions were diagnosed as LR-3 or LR-4 by LI-RADS. Among them, 98 and 152 had "washout" at criteria 1 and 2, respectively. For the diagnosis of HCC, criteria 2 and 3 showed significantly higher sensitivities (67.3 and 92.5%, respectively) compared with criteria 1 (35.5%) (p < 0.001). The specificity of criteria 3 (13%) was significantly lower than those of criteria 1 and 2 (40.7% and 38.4%, respectively, p < 0.001). The specificities between criteria 1 and 2 were not statistically different (p = 0.427). CONCLUSION: Although the LI-RADS lexicon does not permit the interchange of image features among various image modalities, the sensitivity of HCC diagnosis could be improved without any decrease in specificity by adding CT image washout features. ADVANCES IN KNOWLEDGE: Although the LI-RADS lexicon does not permit the interchange of image features among various image modalities, complementary use of dynamic CT in LR-3 or LR-4 categories on the basis of gadoxetic acid-enhanced MRI may contribute to major imaging feature.
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Carcinoma Hepatocelular , Neoplasias Hepáticas , Carcinoma Hepatocelular/diagnóstico por imagen , Medios de Contraste , Gadolinio DTPA , Humanos , Neoplasias Hepáticas/diagnóstico por imagen , Imagen por Resonancia Magnética/métodos , Estudios Retrospectivos , Sensibilidad y Especificidad , Tomografía Computarizada por Rayos XRESUMEN
Research on the chiral magneto-optical properties of inorganic nanomaterials has enabled novel applications in advanced optical and electronic devices. However, the corresponding chiral magneto-optical responses have only been studied under strong magnetic fields of ≥1 T, which limits the wider application of these novel materials. In this paper, we report on the enhanced chiral magneto-optical activity of supra-assembled Fe3O4 magnetite nanoparticles in the visible range at weak magnetic fields of 1.5 mT. The spherical supra-assembled particles with a diameter of â¼90 nm prepared by solvothermal synthesis had single-crystal-like structures, which resulted from the oriented attachment of nanograins. They exhibited superparamagnetic behavior even with a relatively large supraparticle diameter that exceeded the size limit for superparamagnetism. This can be attributed to the small size of nanograins with a diameter of â¼12 nm that constitute the suprastructured particles. Magnetic circular dichroism (MCD) measurements at magnetic fields of 1.5 mT showed distinct chiral magneto-optical activity from charge transfer transitions of magnetite in the visible range. For the supraparticles with lower crystallinity, the MCD peaks in the 250-550 nm range assigned as the ligand-to-metal charge transfer (LMCT) and the inter-sublattice charge transfer (ISCT) show increased intensities in comparison to those with higher crystallinity samples. On the contrary, the higher crystallinity sample shows higher MCD intensities near 600-700 nm for the intervalence charge transfer (IVCT) transition. The differences in MCD responses can be attributed to the crystallinity determined by the reaction time, lattice distortion near grain boundaries of the constituent nanocrystals, and dipolar interactions in the supra-assembled structures.
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Chiral-structured nanoscale materials exhibit chiroptical properties with preferential absorptions of circularly polarized light. The distinctive optical responses of chiral materials have great potential for advanced optical and biomedical applications. However, the fabrication of three-dimensional structures with mirrored nanoscale geometry is still challenging. This study introduces chiral plasmonic nanopatterns in wavy shapes based on the unidirectional alignment of block copolymer thin films and their tilted transfer, combined with buckling processes. The cylindrical nanodomains of polystyrene-block-poly(2-vinylpyridine) thin films were unidirectionally aligned over a large area by the shear-rolling process. The aligned block copolymer thin films were transferred onto uniaxially prestrained polydimethylsiloxane films at certain angles relative to the stretching directions. The strain was then released to induce buckling. The aligned nanopatterns across the axis of the formed microwrinkles were selectively infiltrated with gold ions. After reduction by plasma treatment, chiral plasmonic nanowave patterns were fabricated with the presence of mirror-reflected circular dichroism spectra. This fabrication method does not require any lithography processing or innately chiral biomaterials, which can be advantageous over other conventional fabrication methods for artificial nanoscale chiral materials.