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1.
Nature ; 616(7958): 686-690, 2023 04.
Artigo em Inglês | MEDLINE | ID: mdl-37100940

RESUMO

The nearby radio galaxy M87 is a prime target for studying black hole accretion and jet formation1,2. Event Horizon Telescope observations of M87 in 2017, at a wavelength of 1.3 mm, revealed a ring-like structure, which was interpreted as gravitationally lensed emission around a central black hole3. Here we report images of M87 obtained in 2018, at a wavelength of 3.5 mm, showing that the compact radio core is spatially resolved. High-resolution imaging shows a ring-like structure of [Formula: see text] Schwarzschild radii in diameter, approximately 50% larger than that seen at 1.3 mm. The outer edge at 3.5 mm is also larger than that at 1.3 mm. This larger and thicker ring indicates a substantial contribution from the accretion flow with absorption effects, in addition to the gravitationally lensed ring-like emission. The images show that the edge-brightened jet connects to the accretion flow of the black hole. Close to the black hole, the emission profile of the jet-launching region is wider than the expected profile of a black-hole-driven jet, suggesting the possible presence of a wind associated with the accretion flow.

2.
Nature ; 601(7894): 562-567, 2022 01.
Artigo em Inglês | MEDLINE | ID: mdl-35082417

RESUMO

In conventional superconductors, the phase transition into a zero-resistance and perfectly diamagnetic state is accompanied by a jump in the specific heat and the opening of a spectral gap1. In the high-transition-temperature (high-Tc) cuprates, although the transport, magnetic and thermodynamic signatures of Tc have been known since the 1980s2, the spectroscopic singularity associated with the transition remains unknown. Here we resolve this long-standing puzzle with a high-precision angle-resolved photoemission spectroscopy (ARPES) study on overdoped (Bi,Pb)2Sr2CaCu2O8+δ (Bi2212). We first probe the momentum-resolved electronic specific heat via spectroscopy and reproduce the specific heat peak at Tc, completing the missing link for a holistic description of superconductivity. Then, by studying the full momentum, energy and temperature evolution of the spectra, we reveal that this thermodynamic anomaly arises from the singular growth of in-gap spectral intensity across Tc. Furthermore, we observe that the temperature evolution of in-gap intensity is highly anisotropic in the momentum space, and the gap itself obeys both the d-wave functional form and particle-hole symmetry. These findings support the scenario that the superconducting transition is driven by phase fluctuations. They also serve as an anchor point for understanding the Fermi arc and pseudogap phenomena in underdoped cuprates.

3.
Proc Natl Acad Sci U S A ; 121(14): e2308247121, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38551833

RESUMO

Diamond color centers have proven to be versatile quantum emitters and exquisite sensors of stress, temperature, electric and magnetic fields, and biochemical processes. Among color centers, the silicon-vacancy (SiV[Formula: see text]) defect exhibits high brightness, minimal phonon coupling, narrow optical linewidths, and high degrees of photon indistinguishability. Yet the creation of reliable and scalable SiV[Formula: see text]-based color centers has been hampered by heterogeneous emission, theorized to originate from surface imperfections, crystal lattice strain, defect symmetry, or other lattice impurities. Here, we advance high-resolution cryo-electron microscopy combined with cathodoluminescence spectroscopy and 4D scanning transmission electron microscopy (STEM) to elucidate the structural sources of heterogeneity in SiV[Formula: see text] emission from nanodiamond with sub-nanometer-scale resolution. Our diamond nanoparticles are grown directly on TEM membranes from molecular-level seedings, representing the natural formation conditions of color centers in diamond. We show that individual subcrystallites within a single nanodiamond exhibit distinct zero-phonon line (ZPL) energies and differences in brightness that can vary by 0.1 meV in energy and over 70% in brightness. These changes are correlated with the atomic-scale lattice structure. We find that ZPL blue-shifts result from tensile strain, while ZPL red shifts are due to compressive strain. We also find that distinct crystallites host distinct densities of SiV[Formula: see text] emitters and that grain boundaries impact SiV[Formula: see text] emission significantly. Finally, we interrogate nanodiamonds as small as 40 nm in diameter and show that these diamonds exhibit no spatial change to their ZPL energy. Our work provides a foundation for atomic-scale structure-emission correlation, e.g., of single atomic defects in a range of quantum and two-dimensional materials.

4.
Nat Mater ; 23(6): 775-781, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38182811

RESUMO

The discovery of superconductivity in infinite-layer nickelates established another category of unconventional superconductors that shares structural and electronic similarities with cuprates. However, key issues of the superconducting pairing symmetry, gap amplitude and superconducting fluctuations are yet to be addressed. Here we utilize static and ultrafast terahertz spectroscopy to address these. We demonstrate that the equilibrium terahertz conductivity and non-equilibrium terahertz responses of an optimally Sr-doped nickelate film (superconducting transition temperature of Tc = 17 K) are in line with the electrodynamics of d-wave superconductivity in the dirty limit. The gap-to-Tc ratio (2Δ/kBTc) is found to be 3.4, indicating that the superconductivity falls in the weak coupling regime. In addition, we observed substantial superconducting fluctuations near Tc that do not extend into the deep normal state as the optimally hole-doped cuprates do. Our results support a d-wave system that closely resembles the electron-doped cuprates.

5.
Proc Natl Acad Sci U S A ; 119(32): e2204630119, 2022 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-35914123

RESUMO

The effect of Lifshitz transition on thermodynamics and superconductivity in hole-doped cuprates has been heavily debated but remains an open question. In particular, an observed peak of electronic specific heat is proposed to originate from fluctuations of a putative quantum critical point p* (e.g., the termination of pseudogap at zero temperature), which is close to but distinguishable from the Lifshitz transition in overdoped La-based cuprates where the Fermi surface transforms from hole-like to electron-like. Here we report an in situ angle-resolved photoemission spectroscopy study of three-dimensional Fermi surfaces in La2-xSrxCuO4 thin films (x = 0.06 to 0.35). With accurate kz dispersion quantification, the said Lifshitz transition is determined to happen within a finite range around x = 0.21. Normal state electronic specific heat, calculated from spectroscopy-derived band parameters, reveals a doping-dependent profile with a maximum at x = 0.21 that agrees with previous thermodynamic microcalorimetry measurements. The account of the specific heat maximum by underlying band structures excludes the need for additionally dominant contribution from the quantum fluctuations at p*. A d-wave superconducting gap smoothly across the Lifshitz transition demonstrates the insensitivity of superconductivity to the dramatic density of states enhancement.

6.
Nano Lett ; 24(1): 331-338, 2024 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-38108571

RESUMO

Solar-driven photothermal catalytic H2 production from lignocellulosic biomass was achieved by using 1T-2H MoS2 with tunable Lewis acidic sites as catalysts in an alkaline aqueous solution, in which the number of Lewis acidic sites derived from the exposed Mo edges of MoS2 was successfully regulated by both the formation of an edge-terminated 1T-2H phase structure and tunable layer number. Owing to the abundant Lewis acidic sites for the oxygenolysis of lignocellulosic biomass, the 1T-2H MoS2 catalyst shows high photothermal catalytic lignocellulosic biomass-to-H2 transformation performance in polar wood chips, bamboo, rice straw corncobs, and rice hull aqueous solutions, and the highest H2 generation rate and solar-to-H2 (STH) efficiency respectively achieves 3661 µmol·h-1·g-1 and 0.18% in the polar wood chip system under 300 W Xe lamp illumination. This study provides a sustainable and cost-effective method for the direct transformation of renewable lignocellulosic biomass to H2 fuel driven by solar energy.

7.
Rep Prog Phys ; 87(4)2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38518359

RESUMO

Charge density wave (CDW is one of the most ubiquitous electronic orders in quantum materials. While the essential ingredients of CDW order have been extensively studied, a comprehensive microscopic understanding is yet to be reached. Recent research efforts on the CDW phenomena in two-dimensional (2D) materials provide a new pathway toward a deeper understanding of its complexity. This review provides an overview of the CDW orders in 2D with atomically thin transition metal dichalcogenides (TMDCs) as the materials platform. We mainly focus on the electronic structure investigations on the epitaxially grown TMDC samples with angle-resolved photoemission spectroscopy and scanning tunneling microscopy/spectroscopy as complementary experimental tools. We discuss the possible origins of the 2D CDW, novel quantum states coexisting with them, and exotic types of charge orders that can only be realized in the 2D limit.

8.
J Org Chem ; 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38954507

RESUMO

A three-component strategy was developed to enable hydrodefluoroamination of ß-trifluoromethyl enones by selectively activating two C(sp3)-F bonds in the trifluoromethyl group. The method involved a sequence of carbonyl reduction, hydrodefluorination, and defluoroamination under transition-metal-free conditions. Synthetically useful (E)-stereospecific α-fluoroenamides were obtained in good yields with diverse functional group tolerance, which could be easily transformed into valuable organofluorides and heterocycles. The carbonyl auxiliary exerts both electronic and steric impacts on the CF3-alkenes, allowing for controllable and selective defluorination.

9.
Nature ; 554(7693): 505-510, 2018 02 21.
Artigo em Inglês | MEDLINE | ID: mdl-29469090

RESUMO

Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. However, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistry through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain. We engineer molecules with mechanically heterogeneous components-a compressible ('soft') mechanophore and incompressible ('hard') ligands. In these 'molecular anvils', isotropic stress leads to relative motions of the rigid ligands, anisotropically deforming the compressible mechanophore and activating bonds. Conversely, rigid ligands in steric contact impede relative motion, blocking reactivity. We combine experiments and computations to demonstrate hydrostatic-pressure-driven redox reactions in metal-organic chalcogenides that incorporate molecular elements that have heterogeneous compressibility, in which bending of bond angles or shearing of adjacent chains activates the metal-chalcogen bonds, leading to the formation of the elemental metal. These results reveal an unexplored reaction mechanism and suggest possible strategies for high-specificity mechanosynthesis.

10.
Chem Biodivers ; : e202400934, 2024 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-38898600

RESUMO

Ginseng saponins ( ginsenosides), bioactive compounds derived from ginseng, are widely used natural products with potent therapeutic properties in the management of various ailments, particularly tumors, cardiovascular and cerebrovascular diseases, and immune system disorders. Autophagy, a highly regulated and multistep process involving the breakdown of impaired organelles and macromolecules by autophagolysosomes and autophagy-related genes (ATGs), has gained increasing attention as a potential target for ginsenoside-mediated disease treatment. This review aims to provide a comprehensive overview of recent research advances in the understanding of autophagy-related signaling pathways and the role of ginsenoside-mediated autophagy regulation. By delving into the intricate autophagy signaling pathways underpinning the pharmacological properties of ginsenosides, we highlight their therapeutic potential in addressing various conditions. Our findings serve as a comprehensive reference for further investigation into the medicinal properties of ginseng or ginseng-related products.

11.
Molecules ; 29(4)2024 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-38398583

RESUMO

Hydroxylation of aryl sulfonium salts could be realized by utilizing acetohydroxamic acid and oxime as hydroxylative agents in the presence of cesium carbonate as a base, leading to a variety of structurally diverse hydroxylated arenes in 47-95% yields. In addition, the reaction exhibited broad functionality tolerance, and a range of important functional groups (e.g., cyano, nitro, sulfonyl, formyl, keto, and ester) could be well amenable to the mild reaction conditions.

12.
Molecules ; 29(9)2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38731482

RESUMO

An efficient palladium-catalyzed carbonylation of aryl fluorosulfates with aryl formates for the facile synthesis of esters was developed. The cross-coupling reactions proceeded effectively in the presence of a palladium catalyst, phosphine ligand, and triethylamine in DMF to produce the corresponding esters in moderate to good yields. Of note, functionalities or substituents, such as nitro, cyano, methoxycarbonyl, trifluoromethyl, methylsulfonyl, trifluoromethoxy, fluoro, chloro, bromo, methyl, methoxy, N,N-dimethyl, and [1,3]dioxolyl, were well-tolerated in the reactions, which could be kept for late-stage modification. The reactions employing readily available and relatively robust aryl fluorosulfates as coupling electrophiles could potentially serve as an attractive alternative to traditional cross-couplings with the use of aryl halides and pseudohalides as substrates.

13.
Circulation ; 146(21): 1591-1609, 2022 11 22.
Artigo em Inglês | MEDLINE | ID: mdl-35880522

RESUMO

BACKGROUND: Metabolic disorder increases the risk of abdominal aortic aneurysm (AAA). NRs (nuclear receptors) have been increasingly recognized as important regulators of cell metabolism. However, the role of NRs in AAA development remains largely unknown. METHODS: We analyzed the expression profile of the NR superfamily in AAA tissues and identified NR1D1 (NR subfamily 1 group D member 1) as the most highly upregulated NR in AAA tissues. To examine the role of NR1D1 in AAA formation, we used vascular smooth muscle cell (VSMC)-specific, endothelial cell-specific, and myeloid cell-specific conditional Nr1d1 knockout mice in both AngII (angiotensin II)- and CaPO4-induced AAA models. RESULTS: Nr1d1 gene expression exhibited the highest fold change among all 49 NRs in AAA tissues, and NR1D1 protein was upregulated in both human and murine VSMCs from AAA tissues. The knockout of Nr1d1 in VSMCs but not endothelial cells and myeloid cells inhibited AAA formation in both AngII- and CaPO4-induced AAA models. Mechanistic studies identified ACO2 (aconitase-2), a key enzyme of the mitochondrial tricarboxylic acid cycle, as a direct target trans-repressed by NR1D1 that mediated the regulatory effects of NR1D1 on mitochondrial metabolism. NR1D1 deficiency restored the ACO2 dysregulation and mitochondrial dysfunction at the early stage of AngII infusion before AAA formation. Supplementation with αKG (α-ketoglutarate, a downstream metabolite of ACO2) was beneficial in preventing and treating AAA in mice in a manner that required NR1D1 in VSMCs. CONCLUSIONS: Our data define a previously unrecognized role of nuclear receptor NR1D1 in AAA pathogenesis and an undescribed NR1D1-ACO2 axis involved in regulating mitochondrial metabolism in VSMCs. It is important that our findings suggest αKG supplementation as an effective therapeutic approach for AAA treatment.


Assuntos
Aneurisma da Aorta Abdominal , Humanos , Camundongos , Animais , Aneurisma da Aorta Abdominal/induzido quimicamente , Aneurisma da Aorta Abdominal/genética , Aneurisma da Aorta Abdominal/prevenção & controle , Aorta Abdominal/patologia , Membro 1 do Grupo D da Subfamília 1 de Receptores Nucleares/metabolismo , Músculo Liso Vascular/metabolismo , Ciclo do Ácido Cítrico , Miócitos de Músculo Liso/metabolismo , Angiotensina II/efeitos adversos , Camundongos Knockout , Aconitato Hidratase/metabolismo , Modelos Animais de Doenças , Camundongos Endogâmicos C57BL
14.
Mol Biol Evol ; 39(2)2022 02 03.
Artigo em Inglês | MEDLINE | ID: mdl-34893856

RESUMO

Domestic sheep and their wild relatives harbor substantial genetic variants that can form the backbone of molecular breeding, but their genome landscapes remain understudied. Here, we present a comprehensive genome resource for wild ovine species, landraces and improved breeds of domestic sheep, comprising high-coverage (∼16.10×) whole genomes of 810 samples from 7 wild species and 158 diverse domestic populations. We detected, in total, ∼121.2 million single nucleotide polymorphisms, ∼61 million of which are novel. Some display significant (P < 0.001) differences in frequency between wild and domestic species, or are private to continent-wide or individual sheep populations. Retained or introgressed wild gene variants in domestic populations have contributed to local adaptation, such as the variation in the HBB associated with plateau adaptation. We identified novel and previously reported targets of selection on morphological and agronomic traits such as stature, horn, tail configuration, and wool fineness. We explored the genetic basis of wool fineness and unveiled a novel mutation (chr25: T7,068,586C) in the 3'-UTR of IRF2BP2 as plausible causal variant for fleece fiber diameter. We reconstructed prehistorical migrations from the Near Eastern domestication center to South-and-Southeast Asia and found two main waves of migrations across the Eurasian Steppe and the Iranian Plateau in the Early and Late Bronze Ages. Our findings refine our understanding of genome variation as shaped by continental migrations, introgression, adaptation, and selection of sheep.


Assuntos
Genoma , Carneiro Doméstico , Animais , Ásia , Europa (Continente) , Variação Genética , Irã (Geográfico) , Polimorfismo de Nucleotídeo Único , Análise de Sequência de DNA , Ovinos/genética , Carneiro Doméstico/genética
15.
Phys Rev Lett ; 130(12): 126902, 2023 Mar 24.
Artigo em Inglês | MEDLINE | ID: mdl-37027861

RESUMO

Light-induced ferroelectricity in quantum paraelectrics is a new avenue of achieving dynamic stabilization of hidden orders in quantum materials. In this Letter, we explore the possibility of driving a transient ferroelectric phase in the quantum paraelectric KTaO_{3} via intense terahertz excitation of the soft mode. We observe a long-lived relaxation in the terahertz-driven second harmonic generation (SHG) signal that lasts up to 20 ps at 10 K, which may be attributed to light-induced ferroelectricity. Through analyzing the terahertz-induced coherent soft-mode oscillation and finding its hardening with fluence well described by a single-well potential, we demonstrate that intense terahertz pulses up to 500 kV/cm cannot drive a global ferroelectric phase in KTaO_{3}. Instead, we find the unusual long-lived relaxation of the SHG signal comes from a terahertz-driven moderate dipolar correlation between the defect-induced local polar structures. We discuss the impact of our findings on current investigations of the terahertz-induced ferroelectric phase in quantum paraelectrics.

16.
Hematol Oncol ; 41(2): 230-238, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-35304777

RESUMO

Diffuse large B cell lymphoma (DLBCL) is the most common aggressive lymphoid malignancy, with an immunosuppressive microenvironment affecting clinical outcome. Interleukin (IL)-13 overexpression is observed in multiple solid tumors and contributes to tumor progression. This study aims to investigate pretreatment serum IL-13 levels and their relationship with the prognosis of DLBCL patients. One hundred and sixty-six patients with newly diagnosed DLBCL from June 2015 to July 2017 were included. Patients with elevated pretreatment serum IL-13 levels (IL-13≥1.63 pg/ml) were classified into the high IL-13 group and they had significantly lower complete remission rate (60% vs. 74%, p = 0.0059), higher progression rate (43% vs. 23%, p = 0.0051), and poor progression-free survival (2-year PFS, 63% vs. 78%, p = 0.0078) and overall survival (2-year OS, 75% vs. 92%, p = 0.0027), when compared to those in the low IL-13 group (IL-13<1.63 pg/ml). Meanwhile, increased Treg cell ratio in peripheral blood (p = 0.0147) and elevated serum IL-2 levels (p = 0.0272) were observed in the high IL-13 group. Moreover, RNA sequencing data showed that patients in the high IL-13 group had significantly elevated expression of chemokines and chemokine receptors (CCR4, CCL19, CCL21, CXCL2) related to Treg activation and recruitment. Consistent with the chemokine profile, tumor immunophenotyping analysis revealed that higher Treg cells recruitment in the high IL-13 group than the low IL-13 group (p = 0.0116). In vitro, when lymphoma cells co-cultured with peripheral blood monocytes of healthy controls, metformin down-regulated both IL-13 level and Treg cell ratio, in consistent with the decreased serum IL-13 levels of patients after 6 months of metformin maintenance therapy in the high IL-13 group. Taken together, pretreatment serum IL-13 level is related to the immunosuppressive microenvironment and poor clinical outcome of DLBCL patients and could be targeted by metformin, thus providing a new therapeutic strategy in treating DLBCL with high serum IL-13 levels.


Assuntos
Linfoma Difuso de Grandes Células B , Linfócitos T Reguladores , Humanos , Linfócitos T Reguladores/metabolismo , Linfócitos T Reguladores/patologia , Interleucina-13/metabolismo , Interleucina-13/uso terapêutico , Microambiente Tumoral , Linfoma Difuso de Grandes Células B/tratamento farmacológico , Prognóstico , Progressão da Doença
17.
Langmuir ; 39(21): 7434-7443, 2023 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-37200447

RESUMO

Mn-based catalysts are promising for selective catalytic reduction (SCR) of NOx with NH3 at low temperatures due to their excellent redox capacity. However, the N2 selectivity of Mn-based catalysts is an urgent problem for practical application owing to excessive oxidizability. To solve this issue, we report a Mn-based catalyst using amorphous ZrTiOx as the support (Mn/ZrTi-A) with both excellent low-temperature NOx conversion and N2 selectivity. It is found that the amorphous structure of ZrTiOx modulates the metal-support interaction for anchoring the highly dispersed active MnOx species and constructs a uniquely bridged Mn3+ bonded with the support through oxygen linked to Ti4+ and Zr4+, respectively, which regulates the optimal oxidizability of the MnOx species. As a result, Mn/ZrTi-A is not conducive to the formation of ammonium nitrate that readily decomposes to N2O, thus further increasing N2 selectivity. This work investigates the role of an amorphous support in promoting the N2 selectivity of a manganese-based catalyst and sheds light on the design of efficient low-temperature deNOx catalysts.

18.
Eur Radiol ; 33(12): 8936-8947, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37368104

RESUMO

OBJECTIVES: To evaluate the performance of a radiomics nomogram developed based on gadolinium-ethoxybenzyl-diethylenetriamine penta-acetic acid (Gd-EOB-DTPA) MRI for preoperative prediction of microvascular invasion (MVI) of hepatocellular carcinoma (HCC), and to identify patients who may benefit from the postoperative adjuvant transarterial chemoembolization (PA-TACE). METHODS: A total of 260 eligible patients were retrospectively enrolled from three hospitals (140, 65, and 55 in training, standardized external, and non-standardized external validation cohort). Radiomics features and image characteristics were extracted from Gd-EOB-DTPA MRI image before hepatectomy for each lesion. In the training cohort, a radiomics nomogram which incorporated the radiomics signature and radiological predictors was developed. The performance of the radiomics nomogram was assessed with respect to discrimination calibration, and clinical usefulness with external validation. A score (m-score) was constructed to stratify the patients and explored whether it could accurately predict patient who benefit from PA-TACE. RESULTS: A radiomics nomogram integrated with the radiomics signature, max-D(iameter) > 5.1 cm, peritumoral low intensity (PTLI), incomplete capsule, and irregular morphology had favorable discrimination in the training cohort (AUC = 0.982), the standardized external validation cohort (AUC = 0.969), and the non-standardized external validation cohort (AUC = 0.981). Decision curve analysis confirmed the clinical usefulness of the novel radiomics nomogram. The log-rank test revealed that PA-TACE significantly decreased the early recurrence in the high-risk group (p = 0.006) with no significant effect in the low-risk group (p = 0.270). CONCLUSIONS: The novel radiomics nomogram combining the radiomics signature and clinical radiological features achieved preoperative non-invasive MVI risk prediction and patient benefit assessment after PA-TACE, which may help clinicians implement more appropriate interventions. CLINICAL RELEVANCE STATEMENT: Our radiomics nomogram could represent a novel biomarker to identify patients who may benefit from the postoperative adjuvant transarterial chemoembolization, which may help clinicians to implement more appropriate interventions and perform individualized precision therapies. KEY POINTS: • The novel radiomics nomogram developed based on Gd-EOB-DTPA MRI achieved preoperative non-invasive MVI risk prediction. • An m-score based on the radiomics nomogram could stratify HCC patients and further identify individuals who may benefit from the PA-TACE. • The radiomics nomogram could help clinicians to implement more appropriate interventions and perform individualized precision therapies.


Assuntos
Carcinoma Hepatocelular , Quimioembolização Terapêutica , Neoplasias Hepáticas , Humanos , Carcinoma Hepatocelular/diagnóstico por imagem , Carcinoma Hepatocelular/terapia , Carcinoma Hepatocelular/patologia , Neoplasias Hepáticas/diagnóstico por imagem , Neoplasias Hepáticas/terapia , Neoplasias Hepáticas/irrigação sanguínea , Nomogramas , Estudos Retrospectivos
19.
Chem Rev ; 121(20): 12548-12680, 2021 10 27.
Artigo em Inglês | MEDLINE | ID: mdl-34387465

RESUMO

As the "chemical chameleon", sulfonyl-containing compounds and their variants have been merged with various types of reactions for the efficient construction of diverse molecular architectures by taking advantage of their incredible reactive flexibility. Currently, their involvement in radical transformations, in which the sulfonyl group typically acts as a leaving group via selective C-S, N-S, O-S, S-S, and Se-S bond cleavage/functionalization, has facilitated new bond formation strategies which are complementary to classical two-electron cross-couplings via organometallic or ionic intermediates. Considering the great influence and synthetic potential of these novel avenues, we summarize recent advances in this rapidly expanding area by discussing the reaction designs, substrate scopes, mechanistic studies, and their limitations, outlining the state-of-the-art processes involved in radical-mediated desulfonylation and related transformations. With a specific emphasis on their synthetic applications, we believe this review will be useful for medicinal and synthetic organic chemists who are interested in radical chemistry and radical-mediated desulfonylation in particular.


Assuntos
Elétrons , Técnicas de Química Sintética
20.
Environ Sci Technol ; 57(38): 14472-14481, 2023 09 26.
Artigo em Inglês | MEDLINE | ID: mdl-37695840

RESUMO

Catalyst deactivation caused by alkali metal poisoning has long been a key bottleneck in the application of selective catalytic reduction of NOx with NH3 (NH3-SCR), limiting the service life of the catalyst and increasing the cost of environmental protection. Despite great efforts, continuous accumulation of alkali metal deposition makes the resistance capacity of 2 wt % K2O difficult to enhance via merely loading acid sites on the surface, resulting in rapid deactivation and frequent replacement of the NH3-SCR catalyst. To further improve the resistance of alkali metals, encapsulating alkali metals into the bulk phase could be a promising strategy. The bottleneck of 2 wt % K2O tolerance has been solved by virtue of ultrahigh potassium storage capacity in the amorphous FePO4 bulk phase. Amorphous FePO4 as a support of the NH3-SCR catalyst exhibited a self-adaptive alkali-tolerance mechanism, where potassium ions spontaneously migrated into the bulk phase of amorphous FePO4 and were anchored by PO43- with the generation of Fe2O3 at the NH3-SCR reaction temperature. This ingenious potassium storage mechanism could boost the K2O resistance capacity to 6 wt % while maintaining approximately 81% NOx conversion. Besides, amorphous FePO4 also exhibited excellent resistance to individual and coexistence of alkali (K2O and Na2O), alkali earth (CaO), and heavy metals (PbO and CdO), providing long durability for CePO4/FePO4 catalysts in flue gas with multipollutants. The cheap and accessible amorphous FePO4 paves the way for the development and implementation of poisoning-resistant NOx abatement.


Assuntos
Álcalis , Potássio , Catálise , Temperatura
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