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1.
Nature ; 609(7925): 46-51, 2022 09.
Artículo en Inglés | MEDLINE | ID: mdl-36045238

RESUMEN

Superlattices-a periodic stacking of two-dimensional layers of two or more materials-provide a versatile scheme for engineering materials with tailored properties1,2. Here we report an intrinsic heterodimensional superlattice consisting of alternating layers of two-dimensional vanadium disulfide (VS2) and a one-dimensional vanadium sulfide (VS) chain array, deposited directly by chemical vapour deposition. This unique superlattice features an unconventional 1T stacking with a monoclinic unit cell of VS2/VS layers identified by scanning transmission electron microscopy. An unexpected Hall effect, persisting up to 380 kelvin, is observed when the magnetic field is in-plane, a condition under which the Hall effect usually vanishes. The observation of this effect is supported by theoretical calculations, and can be attributed to an unconventional anomalous Hall effect owing to an out-of-plane Berry curvature induced by an in-plane magnetic field, which is related to the one-dimensional VS chain. Our work expands the conventional understanding of superlattices and will stimulate the synthesis of more extraordinary superstructures.

2.
EMBO J ; 42(15): e111951, 2023 08 01.
Artículo en Inglés | MEDLINE | ID: mdl-37334492

RESUMEN

BRCA1 expression is highly regulated to prevent genomic instability and tumorigenesis. Dysregulation of BRCA1 expression correlates closely with sporadic basal-like breast cancer and ovarian cancer. The most significant characteristic of BRCA1 regulation is periodic expression fluctuation throughout the cell cycle, which is important for the orderly progression of different DNA repair pathways throughout the various cell cycle phases and for further genomic stability. However, the underlying mechanism driving this phenomenon is poorly understood. Here, we demonstrate that RBM10-mediated RNA alternative splicing coupled to nonsense-mediated mRNA decay (AS-NMD), rather than transcription, determines the periodic fluctuations in G1/S-phase BRCA1 expression. Furthermore, AS-NMD broadly regulates the expression of period genes, such as DNA replication-related genes, in an uneconomical but more rapid manner. In summary, we identified an unexpected posttranscriptional mechanism distinct from canonical processes that mediates the rapid regulation of BRCA1 as well as other period gene expression during the G1/S-phase transition and provided insights into potential targets for cancer therapy.


Asunto(s)
Neoplasias de la Mama , Degradación de ARNm Mediada por Codón sin Sentido , Humanos , Femenino , Empalme Alternativo , Empalme del ARN , Neoplasias de la Mama/genética , Inestabilidad Genómica , Proteína BRCA1/genética , Proteínas de Unión al ARN/genética
3.
J Biol Chem ; : 107756, 2024 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-39260699

RESUMEN

Aminoacyl-tRNA synthetases (aaRS) are fundamental to the translation machinery with emerging roles in transcriptional regulation. Previous cellular studies have demonstrated tyrosyl-tRNA synthetase (YARS1 or TyrRS) as a stress response protein through its cytosol-nucleus translocation to maintain cellular homeostasis. Here, we established a mouse model with a disrupted TyrRS nuclear localization signal, revealing its systemic impact on metabolism. Nuclear TyrRS deficiency (YarsΔNLS) led to reduced lean mass, reflecting a mild developmental defect, and reduced fat mass, possibly due to increased energy expenditure. Consistently, YarsΔNLS mice exhibit improved insulin sensitivity and reduced insulin levels, yet maintain normoglycemia, indicative of enhanced insulin action. Notably, YarsΔNLS mice also develop progressive hearing loss. These findings underscore the crucial function of nuclear TyrRS in the maintenance of fat storage and hearing and suggest that aaRSs' regulatory roles can affect metabolic pathways and tissue-specific health. This work broadens our understanding of how protein synthesis interconnects metabolic regulation to ensure energy efficiency.

4.
Small ; : e2311766, 2024 Aug 07.
Artículo en Inglés | MEDLINE | ID: mdl-39109952

RESUMEN

The concept of creating room-temperature ferromagnets from organic radicals proposed nearly sixty years ago, has recently experienced a resurgence due to advances in organic radical chemistry and materials. However, the lack of definitive design paradigms for achieving stable long-range ferromagnetic coupling between organic radicals presents an uncertain future for this research. Here, an innovative strategy is presented to achieve room-temperature ferromagnets by assembling π-conjugated radicals into π-π stacking aggregates. These aggregates, with ultra-close π-π distances and optimal π-π overlap, provide a platform for strong ferromagnetic (FM) interaction. The planar aromatic naphthalene diimide (NDI) anion radicals form nanorod aggregates with a π-π distance of just 3.26 Å, shorter than typical van der Waals distances. The suppressed electron paramagnetic resonance (EPR) signal and emergent near-infrared (NIR) absorption of the aggregates confirm strong interactions between the radicals. Magnetic measurements of NDI anion radical aggregates demonstrate room-temperature ferromagnetism with a saturated magnetization of 1.1 emu g-1, the highest among pure organic ferromagnets. Theoretical calculations reveal that π-stacks of NDI anion radicals with specific interlayer translational slippage favor ferromagnetic coupling over antiferromagnetic coupling.

5.
Small ; 20(21): e2309626, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38098431

RESUMEN

Floating gate memory (FGM), composed of van der Waals (vdW) junctions with an atomically thin floating layer for charge storage, is widely employed to develop logic-in memories and in-sensor computing devices. Most research efforts of FGM are spent on achieving long-term charge storage and fast reading/writing for flash and random-access memory. However, dynamic modulation of memory time via a tunneling barrier and vdW interfaces, which is critical for synaptic computing and machine vision, is still lacking. Here, a van der Waals short-term memory with tunable memory windows and retention times from milliseconds to thousands of seconds is reported, which is approximately exponentially proportional to the thickness h-BN (hexagonal boron nitride) barrier. The specific h-BN barrier with fruitful gap states provides charge release channels for trapped charges, making the vdW device switchable between positive photoconductance and negative photoconductance with a broadband light from IR to UV range. The dynamic short-term memory with tunable photo response highlights the design strategy of novel vdW memory vis interface engineering for further intelligent information storage and optoelectronic detection.

6.
Small ; : e2402182, 2024 Aug 19.
Artículo en Inglés | MEDLINE | ID: mdl-39161191

RESUMEN

Fe-based 2D materials exhibit rich chemical compositions and structures, which may imply many unique physical properties and promising applications. However, achieving controllable preparation of ultrathin non-layered FeS crystal on SiO2/Si substrate remains a challenge. Herein, the influence of temperature and molecular sieves is reported on the synthesis of ultrathin FeS nanosheets with a thickness as low as 2.3 nm by molecular sieves-assisted chemical vapor deposition (CVD). The grown FeS nanosheets exhibit a non-layered hexagonal NiAs structure and belong to the P63/mmc space group. The inverted symmetry broken structure is confirmed by the angle-resolved second harmonic generation (SHG) test. In particular, the 2D FeS nanosheets exhibit exceptional metallic behavior, with conductivity up to 1.63 × 106 S m-1 at 300 K for an 8 nm thick sample, which is higher than that of reported 2D metallic materials. This work provides a significant contribution to the synthesis and characterization of 2D non-layered Fe-based materials.

7.
Nat Mater ; 22(4): 450-458, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-35739274

RESUMEN

Two-dimensional (2D) materials with multiphase, multielement crystals such as transition metal chalcogenides (TMCs) (based on V, Cr, Mn, Fe, Cd, Pt and Pd) and transition metal phosphorous chalcogenides (TMPCs) offer a unique platform to explore novel physical phenomena. However, the synthesis of a single-phase/single-composition crystal of these 2D materials via chemical vapour deposition is still challenging. Here we unravel a competitive-chemical-reaction-based growth mechanism to manipulate the nucleation and growth rate. Based on the growth mechanism, 67 types of TMCs and TMPCs with a defined phase, controllable structure and tunable component can be realized. The ferromagnetism and superconductivity in FeXy can be tuned by the y value, such as superconductivity observed in FeX and ferromagnetism in FeS2 monolayers, demonstrating the high quality of as-grown 2D materials. This work paves the way for the multidisciplinary exploration of 2D TMPCs and TMCs with unique properties.

8.
Chemistry ; 30(8): e202303686, 2024 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-38054967

RESUMEN

Chromophores with hybridized local and charge-transfer (HLCT) excited state are promising for the realization of high performance blue organic light-emitting diodes (OLEDs). The rational manipulation of HLCT excited state for efficient emitters remains challenging. Herein, we present three donor-π-acceptor (D-π-A) molecules (mPAN, mPANPH, and mPNAPH) with phenanthro[9,10-d]imidazole (PI) and pyridinyl as donor and π-bridge respectively. Changes in various kinds of polycyclic aromatic derivative acceptors (anthracene, 9-phenylanthracene, and 1-phenylnaphthalene) could manipulate the excited states and optoelectronic properties. Theoretical calculations reveal that the S1 state of mPNAPH exhibits HLCT nature while the other two molecules show local excited (LE) state dominated feature. The photophysical properties also demonstrate this characteristic. Therefore, compared with mPAN and mPANPH, mPNAPH has higher photoluminescence quantum yield (PLQY) whether in solutions or neat films. Ultimately, the non-doped devices based on these emitters show high luminance larger than 35000 cd m-2 , and high maximum external quantum efficiencies (EQEmax s) larger than 5 % with low efficiency roll-off. In particular, the mPNAPH-based device displays an excellent performance of pure blue emission at 456 nm with Commission Internationale de L'Eclairage coordinate of (0.15, 0.16) and EQEmax of 6.13 % that benefited from the HLCT state and high-lying reverse intersystem crossing process.

9.
Chemistry ; 30(2): e202302943, 2024 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-37803935

RESUMEN

Excellent stability is an essential premise for organic diradicals to be used in organic electronic and spintronic devices. We have attached two tris(2,4,6-trichlorophenyl)methyl (TTM) radical building blocks to the two sides of perylene bisimide (PBI) bridges and obtained two regioisomeric diradicals (1,6-TTM-PBI and 1,7-TTM-PBI). Both of the isomers show super stability rather than the monomeric TTM under ambient conditions, due to the increased conjugation and the electron-withdrawing effects of the PBI bridges. The diradicals show distinct and reversible multistep redox processes, and a spectro-electrochemistry investigation revealed the generation of organic mixed-valence (MV) species during reduction processes. The two diradicals have singlet ground states, very small singlet-triplet energy gaps (ΔES-T ) and a pure open-shell character (with diradical character y0 =0.966 for 1,6-TTM-PBI and 0.967 for 1,7-TTM-PBI). This work opens a window to developing very stable diradicals and offers the opportunity of their further application in optical, electronic and magnetic devices.

10.
Nature ; 556(7701): 355-359, 2018 04.
Artículo en Inglés | MEDLINE | ID: mdl-29670263

RESUMEN

Investigations of two-dimensional transition-metal chalcogenides (TMCs) have recently revealed interesting physical phenomena, including the quantum spin Hall effect1,2, valley polarization3,4 and two-dimensional superconductivity 5 , suggesting potential applications for functional devices6-10. However, of the numerous compounds available, only a handful, such as Mo- and W-based TMCs, have been synthesized, typically via sulfurization11-15, selenization16,17 and tellurization 18 of metals and metal compounds. Many TMCs are difficult to produce because of the high melting points of their metal and metal oxide precursors. Molten-salt-assisted methods have been used to produce ceramic powders at relatively low temperature 19 and this approach 20 was recently employed to facilitate the growth of monolayer WS2 and WSe2. Here we demonstrate that molten-salt-assisted chemical vapour deposition can be broadly applied for the synthesis of a wide variety of two-dimensional (atomically thin) TMCs. We synthesized 47 compounds, including 32 binary compounds (based on the transition metals Ti, Zr, Hf, V, Nb, Ta, Mo, W, Re, Pt, Pd and Fe), 13 alloys (including 11 ternary, one quaternary and one quinary), and two heterostructured compounds. We elaborate how the salt decreases the melting point of the reactants and facilitates the formation of intermediate products, increasing the overall reaction rate. Most of the synthesized materials in our library are useful, as supported by evidence of superconductivity in our monolayer NbSe2 and MoTe2 samples21,22 and of high mobilities in MoS2 and ReS2. Although the quality of some of the materials still requires development, our work opens up opportunities for studying the properties and potential application of a wide variety of two-dimensional TMCs.

11.
Small ; 19(30): e2302314, 2023 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-37191278

RESUMEN

Increasing the relative dielectric constant is a constant pursuit of organic semiconductors, but it often leads to multiple changes in device characteristics, hindering the establishment of a reliable relationship between dielectric constant and photovoltaic performance. Herein, a new non-fullerene acceptor named BTP-OE is reported by replacing the branched alkyl chains on Y6-BO with branched oligoethylene oxide chains. This replacement successfully increases the relative dielectric constant from 3.28 to 4.62. To surprise, BTP-OE offers consistently lower device performance relative to Y6-BO in organic solar cells (16.27% vs 17.44%) due to the losses in open-circuit voltage and fill factor. Further investigations unravel that BTP-OE has resulted in reduced electron mobility, increased trap density, enhanced first order recombination, and enlarged energetic disorder. These results demonstrate the complex relationship between dielectric constant and device performance, which provide valuable implications for the development of organic semiconductors with high dielectric constant for photovoltaic application.

12.
Phys Rev Lett ; 130(16): 166702, 2023 Apr 21.
Artículo en Inglés | MEDLINE | ID: mdl-37154646

RESUMEN

The anomalous Hall effect (AHE), a protocol of various low-power dissipation quantum phenomena and a fundamental precursor of intriguing topological phases of matter, is usually observed in ferromagnetic materials with an orthogonal configuration between the electric field, magnetization, and the Hall current. Here, based on the symmetry analysis, we find an unconventional AHE induced by the in-plane magnetic field (IPAHE) via the spin-canting effect in PT-symmetric antiferromagnetic (AFM) systems, featuring a linear dependence of magnetic field and 2π angle periodicity with a comparable magnitude to conventional AHE. We demonstrate the key findings in the known AFM Dirac semimetal CuMnAs and a new kind of AFM heterodimensional VS_{2}-VS superlattice with a nodal-line Fermi surface and, also, briefly discuss the experimental detection. Our Letter provides an efficient pathway for searching and/or designing realistic materials for a novel IPAHE that could greatly facilitate their application in AFM spintronic devices. National Science Foundation.

14.
Proc Natl Acad Sci U S A ; 117(45): 28239-28250, 2020 11 10.
Artículo en Inglés | MEDLINE | ID: mdl-33109719

RESUMEN

Aberrant programmed cell death protein 1 (PD-1) expression on the surface of T cells is known to inhibit T cell effector activity and to play a pivotal role in tumor immune escape; thus, maintaining an appropriate level of PD-1 expression is of great significance. We identified KLHL22, an adaptor of the Cul3-based E3 ligase, as a major PD-1-associated protein that mediates the degradation of PD-1 before its transport to the cell surface. KLHL22 deficiency leads to overaccumulation of PD-1, which represses the antitumor response of T cells and promotes tumor progression. Importantly, KLHL22 was markedly decreased in tumor-infiltrating T cells from colorectal cancer patients. Meanwhile, treatment with 5-fluorouracil (5-FU) could increase PD-1 expression by inhibiting the transcription of KLHL22. These findings reveal that KLHL22 plays a crucial role in preventing excessive T cell suppression by maintaining PD-1 expression homeostasis and suggest the therapeutic potential of 5-FU in combination with anti-PD-1 in colorectal cancer patients.


Asunto(s)
Proteínas Adaptadoras Transductoras de Señales/metabolismo , Homeostasis , Receptor de Muerte Celular Programada 1/metabolismo , Linfocitos T/inmunología , Proteínas Adaptadoras Transductoras de Señales/efectos de los fármacos , Proteínas Adaptadoras Transductoras de Señales/genética , Animales , Linfocitos T CD4-Positivos/metabolismo , Linfocitos T CD8-positivos/inmunología , Fluorouracilo , Células HEK293 , Humanos , Proteínas de Punto de Control Inmunitario , Masculino , Ratones , Ratones Endogámicos C57BL , Ratones Noqueados , Proteolisis , Transducción de Señal , Transcriptoma , Microambiente Tumoral/inmunología , Ubiquitina-Proteína Ligasas/metabolismo
15.
Nano Lett ; 22(3): 1190-1197, 2022 Feb 09.
Artículo en Inglés | MEDLINE | ID: mdl-35043640

RESUMEN

Construction of lateral junctions is essential to generate one-dimensional (1D) confined potentials that can effectively trap quasiparticles. A series of remarkable electronic phases in one dimension, such as Wigner crystallization, are expected to be realized in such junctions. Here, we demonstrate that we can precisely tune the 1D-confined potential with an in situ manipulation technique, thus providing a dynamic way to modify the correlated electronic states at the junctions. We confirm the existence of 1D-confined potential at the homojunction of two single-layer 1T-NbSe2 islands. Such potential is structurally sensitive and shows a nonmonotonic function of their interspacing. Moreover, there is a change of electronic properties from the correlated insulator to the generalized 1D Wigner crystallization while the confinement becomes strong. Our findings not only establish the capability to fabricate structures with dynamically tunable properties, but also pave the way toward more exotic correlated systems in low dimensions.

16.
Nano Lett ; 22(1): 203-210, 2022 Jan 12.
Artículo en Inglés | MEDLINE | ID: mdl-34928607

RESUMEN

The burgeoning field of twistronics, which concerns how changing the relative twist angles between two materials creates new optoelectronic properties, offers a novel platform for studying twist-angle dependent excitonic physics. Herein, by surveying a range of hexagonal phase transition metal dichalcogenides (TMD) twisted homobilayers, we find that 21.8 ± 1.0°-twisted (7a×7a) and 27.8 ± 1.0°-twisted (13a×13a) bilayers account for nearly 20% of the total population of twisted bilayers in solution-phase restacked bilayers and can be found also in chemical vapor deposition (CVD) samples. Examining the optical properties associated with these twisted angles, we found that 21.8 ± 1.0° twisted MoS2 bilayers exhibit an intense moiré exciton peak in the photoluminescence (PL) spectra, originating from the refolded Brillouin zones. Our work suggests that commensurately twisted TMD homobilayers with short commensurate wavelengths can have interesting optoelectronic properties that are different from the small twist angle counterparts.

17.
Small ; 18(13): e2105215, 2022 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-34923740

RESUMEN

Layered metal chalcogenides, as a "rich" family of 2D materials, have attracted increasing research interest due to the abundant choices of materials with diverse structures and rich electronic characteristics. Although the common metal chalcogenide phases such as 2H and 1T have been intensively studied, many other unusual phases are rarely explored, and some of these show fascinating behaviors including superconductivity, ferroelectrics, ferromagnetism, etc. From this perspective, the unusual phases of metal chalcogenides and their characteristics, as well as potential applications are introduced. First, the unusual phases of metal chalcogenides from different classes, including transition metal dichalcogenides, magnetic element-based chalcogenides, and metal phosphorus chalcogenides, are discussed, respectively. Meanwhile, their excellent properties of different unusual phases are introduced. Then, the methods for producing the unusual phases are discussed, specifically, the stabilization strategies during the chemical vapor deposition process for the unusual phase growth are discussed, followed by an outlook and discussions on how to prepare the unusual phase metal dichalcogenides in terms of synthetic methodology and potential applications.

18.
Chemistry ; 28(29): e202200770, 2022 May 19.
Artículo en Inglés | MEDLINE | ID: mdl-35388924

RESUMEN

A starlike heterocyclic molecule containing an electron-deficient nonaaza-core structure and three peripheral isoquinolines locked by three tetracoordinate borons, namely isoquinoline-nona-starazine (QNSA), is synthesized by using readily available reactants through a rather straightforward approach. This new heteroatom-rich QNSA possesses a quasi-planar π-backbone structure, and bears phenyl substituents on borons which protrude on both sides of the π-backbones endowing it with good solubility in common organic solvents. Contrasting to its starphene analogue, QNSA shows intense fluorescence with a quantum yield (PLQY) of up to 62 % in dilute solution.

19.
Nano Lett ; 21(14): 6014-6021, 2021 Jul 28.
Artículo en Inglés | MEDLINE | ID: mdl-34236873

RESUMEN

Grain boundaries (GBs) are vital to crystal materials and their applications. Although GBs in bulk and two-dimensional materials have been extensively studied, the segmented GBs observed in transition metal dichalcogenide monolayers by a sequence of folded segments remain a mystery. We visualize the large-area distribution of the segmented GBs in MoSe2 monolayers and unravel their structural origin using ab initio calculations combined with high-resolution atomic characterizations. Unlike normal GBs in two-dimensional materials with commonly one type of dislocation cores, the segmented GBs consist of two basic elements-4|8 and 4|4|8 cores, whose alloying results in structural diversity and distinctly high stability due to relieved stress fields nearby. The defective polygons can uniquely migrate along the segmented GBs via the movement of single molybdenum atoms, unobtrusively endowing a given GB with variable appearances. Furthermore, the segmented GBs can achieve useful functionalities such as intrinsic magnetism and highly active electrocatalysis.

20.
Angew Chem Int Ed Engl ; 61(35): e202209343, 2022 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-35816355

RESUMEN

Highly efficient organic thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) emitters for organic light-emitting diodes (OLEDs) generally consist of a twisted donor-acceptor skeleton with aromatic amine donors. Herein, through introducing sulfur atoms into isomeric pentaphene and pentacene frameworks, we demonstrate a set of polycyclic luminophores exhibiting efficient TADF and RTP characters. The incorporation of sulfur atoms confirms a folded molecular plane, while intensifies singlet-triplet spin-orbit coupling. Further, the isomeric effect has a significant effect on the electronic structure of excited state, giving rise to the investigated compounds tunable luminescence mechanisms of TADF and RTP. With efficient triplet harvesting ability, maximum external quantum efficiencies up to 25.1 % and 8.7 % are achieved for the corresponding TADF and RTP OLEDs, verifying the great potential of sulfur-bridged frameworks for highly efficient devices.

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