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1.
Phys Chem Chem Phys ; 26(36): 23600-23608, 2024 Sep 18.
Artículo en Inglés | MEDLINE | ID: mdl-39246268

RESUMEN

Topological semimetals have garnered significant interest due to their intrinsic topological physics and potential applications in devices. A crucial feature shared by all topological materials is the bulk-boundary correspondence, indicating the presence of unique topologically protected conducting states at the edges when non-trivial band topology exists in the bulk. Previous studies on surface states of topological materials predominantly focused on pristine surfaces, leaving the exploration of surface states in topological semimetals with adsorbates relatively uncharted. This work, based on ab initio calculations, examines variations in the topological surface states of MgB2, a well-known conventional superconductor and topological nodal line semimetal. We employ a thick slab model with Mg/B atoms as surface terminations to simulate its topological surface states. Subsequently, we investigate the adsorption of hydrogen (H), hydroxide (OH), and water (H2O) on the surface slabs to observe changes in the surface states. The pristine slab model gives the drumhead-like surface states inside the surface projected nodal lines, while the topological surface states change differently after adsorbing H, OH, and H2O, which can be understood systematically by combining the surface adsorption Gibbs free energy ΔG, surface terminations, and surface charge density distributions. Especially, our findings suggest that the Bader charge transfer value of surface atoms providing topological states is a key indicator for evaluating the variation in topological surface states after adsorption. This study provides a systematic understanding of the topological surface states of MgB2 with different adsorbates, paving the way for future theoretical and experimental investigations in related fields and shedding light on the potential device applications of topological materials.

2.
Sci Rep ; 14(1): 16345, 2024 Jul 16.
Artículo en Inglés | MEDLINE | ID: mdl-39014093

RESUMEN

During rock drilling, a drill bit will wear as it breaks the rock. However, there is no uniform grading standard for rock abrasiveness. To solve this problem, the wear mechanisms of a polycrystalline diamond compact (PDC) bit and the formation it is drilling into are analyzed in depth, and an abrasiveness evaluation method based on the fractal dimension of the rock surface topography is established. Initially, a three-dimensional digital model is generated from a scanning electron microscope image of the rock after drilling; next, an evaluation of the irregularities on the rock surface is performed using an adapted Weierstrass-Mandelbrot (W-M) function to ascertain the fractal dimensionality. Then, the microcontact characteristics of the contact surface between the formation and the PDC bit are analyzed, and the distribution of the microconvex contact points of the two-body friction pair in a region is obtained. Because the sliding friction between the drill bit and the rock produces a large amount of heat, according to the contact area formula of the friction surface and heat conduction theory, the temperature rise and overall temperature distribution of the formation and PDC bit under the condition of sliding friction are revealed, and the real contact area between the formation and the drill bit within a certain temperature range is obtained. Finally, the evaluation index of rock abrasiveness under sliding conditions is established by adopting the wear weight loss of the rock cutting tool per unit volume as the index of rock abrasiveness, and the model is verified by a microdrilling experiment. The research in this paper is highly important for improving the rock-breaking efficiency and bit service life during drilling.

3.
ACS Appl Mater Interfaces ; 16(27): 34840-34849, 2024 Jul 10.
Artículo en Inglés | MEDLINE | ID: mdl-38946061

RESUMEN

Adopting noble metals on non-noble metals is an effective strategy to balance the cost and activity of electrocatalysts. Herein, a thorough analysis of the synergistic OER is conducted at the heterogeneous interface formed by Ir clusters and NiCo2O4 based on DFT calculations. Specifically, the electrons spontaneously bring an eg occupancy of interfacial Ir close to unity after the absorbed O, providing more transferable electrons for the conversion of the absorbed O-intermediates. Besides, the diffuse distribution of electrons in the Ir 5d orbital fills the antibonding orbital after O is absorbed, avoiding the desorption difficulties caused by the stronger Ir-O bonds. The electrons transfer from Ir to Co atoms at the heterogeneous interface and fill the Co 3d band near the Fermi level, stimulating the interfacial Co to participate in the direct O-O coupling (DOOC) pathway. Experimentally, the ultrathin-modulated NiCo2O4 nanosheets are used to support Ir clusters (Ircluster-E-NiCo2O4) by the electrodeposition method. The as-synthesized Ircluster-E-NiCo2O4 catalyst achieves a current density of 10 mA cm-2 at an ultralow overpotential of 238 mV and works steadily for 100 h under a high current of 100 mA cm-2, benefiting from the efficient DOOC pathway during the OER.

4.
Angew Chem Int Ed Engl ; 63(34): e202407838, 2024 Aug 19.
Artículo en Inglés | MEDLINE | ID: mdl-38860437

RESUMEN

The inherent chiral structures of DNA serve as attractive scaffolds to construct DNA hybrid catalysts for valuable enantioselective transformations. Duplex and G-quadruplex DNA-based enantioselective catalysis has made great progress, yet novel design strategies of DNA hybrid catalysts are highly demanding and atomistic analysis of active centers is still challenging. DNA i-motif structures could be finely tuned by different cytosine-cytosine base pairs, providing a new platform to design DNA catalysts. Herein, we found that a human telomeric i-motif DNA containing cytosine-silver(I)-cytosine (C-Ag+-C) base pairs interacting with Cu(II) ions (i-motif DNA(Ag+)/Cu2+) could catalyze Diels-Alder reactions with full conversions and up to 95 % enantiomeric excess. As characterized by various physicochemical techniques, the presence of Ag+ is proved to replace the protons in hemiprotonated cytosine-cytosine (C : C+) base pairs and stabilize the DNA i-motif to allow the acceptance of Cu(II) ions. The i-motif DNA(Ag+)/Cu2+ catalyst shows about 8-fold rate acceleration compared with DNA and Cu2+. Based on DNA mutation experiments, thermodynamic studies and density function theory calculations, the catalytic center of Cu(II) ion is proposed to be located in a specific loop region via binding to one nitrogen-7 atom of an unpaired adenine and two phosphate-oxygen atoms from nearby deoxythymidine monophosphate and deoxyadenosine monophosphate, respectively.


Asunto(s)
Cobre , Reacción de Cicloadición , ADN , Plata , Plata/química , Catálisis , ADN/química , Estereoisomerismo , Cobre/química , Citosina/química , Humanos , Emparejamiento Base
5.
Adv Sci (Weinh) ; 11(29): e2308769, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38810124

RESUMEN

Cardiac hypertrophy is a key factor driving heart failure (HF), yet its pathogenesis remains incompletely elucidated. Mettl1-catalyzed RNA N7-methylguanosine (m7G) modification has been implicated in ischemic cardiac injury and fibrosis. This study aims to elucidate the role of Mettl1 and the mechanism underlying non-ischemic cardiac hypertrophy and HF. It is found that Mettl1 is upregulated in human failing hearts and hypertrophic murine hearts following transverse aortic constriction (TAC) and Angiotensin II (Ang II) infusion. YY1 acts as a transcriptional factor for Mettl1 during cardiac hypertrophy. Mettl1 knockout alleviates cardiac hypertrophy and dysfunction upon pressure overload from TAC or Ang II stimulation. Conversely, cardiac-specific overexpression of Mettl1 results in cardiac remodeling. Mechanically, Mettl1 increases SRSF9 expression by inducing m7G modification of SRSF9 mRNA, facilitating alternative splicing and stabilization of NFATc4, thereby promoting cardiac hypertrophy. Moreover, the knockdown of SRSF9 protects against TAC- or Mettl1-induced cardiac hypertrophic phenotypes in vivo and in vitro. The study identifies Mettl1 as a crucial regulator of cardiac hypertrophy, providing a novel therapeutic target for HF.


Asunto(s)
Cardiomegalia , Modelos Animales de Enfermedad , Animales , Humanos , Masculino , Ratones , Cardiomegalia/genética , Cardiomegalia/metabolismo , Metiltransferasas/metabolismo , Metiltransferasas/genética , Ratones Endogámicos C57BL , Ratones Noqueados , Factores de Transcripción NFATC/metabolismo , Factores de Transcripción NFATC/genética , Factores de Empalme Serina-Arginina/metabolismo , Factores de Empalme Serina-Arginina/genética
6.
Adv Mater ; 36(26): e2401486, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38607186

RESUMEN

Aqueous electrolytes and related aqueous rechargeable batteries own unique advantage on safety and environmental friendliness, but coupling high energy density Li-metal batteries with aqueous electrolyte still represent challenging and not yet reported. Here, this work makes a breakthrough in "high-voltage aqueous Li-metal batteries" (HVALMBs) by adopting a brilliant hybrid-electrolytes strategy. Concentrated ternary-salts ether-based electrolyte (CTE) acts as the anolyte to ensure the stability and reversibility of Li-metal plating/stripping. Eco-friendly water-in-salt (WiS) electrolyte acts as catholyte to support the healthy operation of high-voltage cathodes. Most importantly, the aqueous catholyte and non-aqueous anolyte are isolated in each independent chamber without any crosstalk. Aqueous catholyte permeation toward Li anode can be completely prohibited without proton-induced corrosion, which is enabled by the introduction of under-liquid dual super-lyophobic membrane-based separator, which can realize the segregation of the most effective immiscible electrolytes with a surface tension difference as small as 6 mJ m-2. As a result, the aqueous electrolyte can be successfully coupled with Li-metal anode and achieve the fabrication of HVALMBs (hybrid-electrolytes system), which presents long-term cycle stability with a capacity retention of 81.0% after 300 cycles (LiNi0.8Mn0.1Co0.1O2 || Li (limited) cell) and high energy density (682 Wh kg-1).

7.
Redox Biol ; 72: 103145, 2024 06.
Artículo en Inglés | MEDLINE | ID: mdl-38583415

RESUMEN

Ferroptosis is a nonapoptotic form of regulated cell death that has been reported to play a central role in cardiac ischemia‒reperfusion (I/R) injury. N-acetyltransferase 10 (NAT10) contributes to cardiomyocyte apoptosis by functioning as an RNA ac4c acetyltransferase, but its role in cardiomyocyte ferroptosis during I/R injury has not been determined. This study aimed to elucidate the role of NAT10 in cardiac ferroptosis as well as the underlying mechanism. The mRNA and protein levels of NAT10 were increased in mouse hearts after I/R and in cardiomyocytes that were exposed to hypoxia/reoxygenation. P53 acted as an endogenous activator of NAT10 during I/R in a transcription-dependent manner. Cardiac overexpression of NAT10 caused cardiomyocyte ferroptosis to exacerbate I/R injury, while cardiomyocyte-specific knockout of NAT10 or pharmacological inhibition of NAT10 with Remodelin had the opposite effects. The inhibition of cardiomyocyte ferroptosis by Fer-1 exerted superior cardioprotective effects against the NAT10-induced exacerbation of post-I/R cardiac damage than the inhibition of apoptosis by emricasan. Mechanistically, NAT10 induced the ac4C modification of Mybbp1a, increasing its stability, which in turn activated p53 and subsequently repressed the transcription of the anti-ferroptotic gene SLC7A11. Moreover, knockdown of Mybbp1a partially abolished the detrimental effects of NAT10 overexpression on cardiomyocyte ferroptosis and cardiac I/R injury. Collectively, our study revealed that p53 and NAT10 interdependently cooperate to form a positive feedback loop that promotes cardiomyocyte ferroptosis to exacerbate cardiac I/R injury, suggesting that targeting the NAT10/Mybbp1a/p53 axis may be a novel approach for treating cardiac I/R.


Asunto(s)
Ferroptosis , Daño por Reperfusión Miocárdica , Miocitos Cardíacos , Proteína p53 Supresora de Tumor , Animales , Humanos , Masculino , Ratones , Acetiltransferasas/metabolismo , Acetiltransferasas/genética , Apoptosis , Modelos Animales de Enfermedad , Retroalimentación Fisiológica , Ferroptosis/genética , Daño por Reperfusión Miocárdica/metabolismo , Daño por Reperfusión Miocárdica/patología , Daño por Reperfusión Miocárdica/genética , Miocitos Cardíacos/metabolismo , Miocitos Cardíacos/patología , Transducción de Señal , Proteína p53 Supresora de Tumor/metabolismo , Proteína p53 Supresora de Tumor/genética
8.
ACS Appl Mater Interfaces ; 16(13): 16050-16061, 2024 Apr 03.
Artículo en Inglés | MEDLINE | ID: mdl-38512022

RESUMEN

The distinctive characteristics of alloy catalysts, encompassing composition, structure, and modifiable adsorption sites, present significant potential for the development of highly efficient electrocatalysts for oxygen evolution/reduction reactions [oxygen evolution reactions (OERs)/oxygen reduction reactions (ORRs)]. Machine learning (ML) methods can quickly establish the relationship between material features and catalytic activity, thus accelerating the development of alloy electrocatalysts. However, the current abundance of features presents a crucial challenge in selecting the most pertinent ones. In this study, we explored seven intrinsic features directly derived from the material's structure, with a specific focus on the chemical environment of active sites and their nearest neighbors. An accurate and efficient ML model to predict potential bifunctional oxygen electrocatalysts based on the intrinsic features of AB-type alloy active sites and intermediate free energies in the OERs/ORRs was established. These features possess clear physical and chemical meanings, closely linked to the electronic and geometric structures of active sites and neighboring atoms, thereby providing indispensable insights for the discovery of high-performance electrocatalysts. The ML model achieved R2 scores of 0.827, 0.913, and 0.711 for the predicted values of the three intermediate (OH, O, OOH) free energies, with corresponding mean absolute errors of 0.175, 0.242, and 0.200 eV, respectively. These results indicate that the ML model exhibits high accuracy in predicting the intermediate free energies. Furthermore, the ML model exhibited a prediction efficiency 150,000 times faster than traditional density functional theory calculations. This work will offer valuable insights and a framework for facilitating the rapid design of potential catalysts by ML methods.

9.
Acad Radiol ; 31(5): 2074-2084, 2024 05.
Artículo en Inglés | MEDLINE | ID: mdl-38185571

RESUMEN

RATIONALE AND OBJECTIVES: This study employed tract-based spatial statistics (TBSS) to investigate abnormalities in the white matter microstructure among children with autism spectrum disorder (ASD). Additionally, an eXtreme Gradient Boosting (XGBoost) model was developed to effectively classify individuals with ASD and typical developing children (TDC). METHODS AND MATERIALS: Multi-shell diffusion weighted images were acquired from 62 children with ASD and 44 TDC. Using the Pydesigner procedure, diffusion tensor (DT), diffusion kurtosis (DK), and white matter tract integrity (WMTI) metrics were computed. Subsequently, TBSS analysis was applied to discern differences in these diffusion parameters between ASD and TDC groups. The XGBoost model was then trained using metrics showing significant differences, and Shapley Additive explanations (SHAP) values were computed to assess the feature importance in the model's predictions. RESULTS: TBSS analysis revealed a significant reduction in axonal diffusivity (AD) in the left posterior corona radiata and the right superior corona radiata. Among the DK indicators, mean kurtosis, axial kurtosis, and kurtosis fractional anisotropy were notably increased in children with ASD, with no significant difference in radial kurtosis. WMTI metrics such as axonal water fraction, axonal diffusivity of the extra-axonal space (EAS_AD), tortuosity of the extra-axonal space (EAS_TORT), and diffusivity of intra-axonal space (IAS_Da) were significantly increased, primarily in the corpus callosum and fornix. Notably, there was no significant difference in radial diffusivity of the extra-axial space (EAS_RD). The XGBoost model demonstrated excellent classification ability, and the SHAP analysis identified EAS_TORT as the feature with the highest importance in the model's predictions. CONCLUSION: This study utilized TBSS analyses with multi-shell diffusion data to examine white matter abnormalities in pediatric autism. Additionally, the developed XGBoost model showed outstanding performance in classifying ASD and TDC. The ranking of SHAP values based on the XGBoost model underscored the significance of features in influencing model predictions.


Asunto(s)
Trastorno del Espectro Autista , Imagen de Difusión Tensora , Aprendizaje Automático , Sustancia Blanca , Humanos , Trastorno del Espectro Autista/diagnóstico por imagen , Trastorno del Espectro Autista/patología , Sustancia Blanca/diagnóstico por imagen , Sustancia Blanca/patología , Masculino , Femenino , Preescolar , Imagen de Difusión Tensora/métodos , Imagen de Difusión por Resonancia Magnética/métodos , Niño , Interpretación de Imagen Asistida por Computador/métodos
10.
Int J Biol Macromol ; 253(Pt 3): 126973, 2023 Dec 31.
Artículo en Inglés | MEDLINE | ID: mdl-37729988

RESUMEN

Ferritin possesses a stable and uniform cage structure, along with tumor-targeting properties and excellent biocompatibility, making it a promising drug delivery vehicle. However, the current ferritin drug loading strategy involves complex steps and harsh reaction conditions, resulting in low yield and recovery of drug loading, which limits the clinical application prospects of ferritin nanomedicine. In this study, we utilized the high-efficiency heat-sensitivity of the multiple channel switch structures of the E-helix-cut ferritin mutant (Ecut-HFn) and Cu2+ assistance to achieve high-efficiency loading of chemotherapeutic drugs in a one-step process at low temperatures. This method features mild reaction conditions (45 °C), high loading efficiency (about 110 doxorubicin (Dox) per Ecut-HFn), and improved protein and Dox recovery rates (with protein recovery rate around 94 % and Dox recovery rate reaching up to 45 %). The prepared ferritin-Dox particles (Ecut-HFn-Cu-Dox) exhibit a uniform size distribution, good stability, and retain the natural tumor targeting ability of ferritin. Overall, this temperature-controlled drug loading strategy utilizing heat-sensitivity ferritin mutants is energy-saving, environmentally friendly, efficient, and easy to operate, offering a new perspective for scaling up the industrial production of ferritin drug carriers.


Asunto(s)
Antineoplásicos , Nanopartículas , Neoplasias , Humanos , Antineoplásicos/química , Ferritinas/genética , Ferritinas/química , Calor , Doxorrubicina/química , Neoplasias/tratamiento farmacológico , Portadores de Fármacos/química , Sistemas de Liberación de Medicamentos , Nanopartículas/química
11.
Sci China Life Sci ; 66(12): 2786-2804, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37450238

RESUMEN

Ischemic heart failure (HF) remains a leading cause of morbidity and mortality. Maintaining homeostasis of cardiac function and preventing cardiac remodeling deterioration are critical to halting HF progression. Methyltransferase-like protein 13 (Mettl13) has been shown to regulate protein translation efficiency by acting as a protein lysine methyltransferase, but its role in cardiac pathology remains unexplored. This study aims to characterize the roles and mechanisms of Mettl13 in cardiac contractile function and HF. We found that Mettl13 was downregulated in the failing hearts of mice post-myocardial infarction (MI) and in a cellular model of oxidative stress. Cardiomyocyte-specific overexpression of Mettl13 mediated by AAV9-Mettl13 attenuated cardiac contractile dysfunction and fibrosis in response to MI, while silencing of Mettl13 impaired cardiac function in normal mice. Moreover, Mettl13 overexpression abrogated the reduction in cell shortening, Ca2+ transient amplitude and SERCA2a protein levels in the cardiomyocytes of adult mice with MI. Conversely, knockdown of Mettl13 impaired the contractility of cardiomyocytes, and decreased Ca2+ transient amplitude and SERCA2a protein expression in vivo and in vitro. Mechanistically, Mettl13 impaired the stability of c-Cbl by inducing lysine methylation of c-Cbl, which in turn inhibited ubiquitination-dependent degradation of SERCA2a. Furthermore, the inhibitory effects of knocking down Mettl13 on SERCA2a protein expression and Ca2+ transients were partially rescued by silencing c-Cbl in H2O2-treated cardiomyocytes. In conclusion, our study uncovers a novel mechanism that involves the Mettl13/c-Cbl/SERCA2a axis in regulating cardiac contractile function and remodeling, and identifies Mettl13 as a novel therapeutic target for ischemic HF.


Asunto(s)
Insuficiencia Cardíaca , Peróxido de Hidrógeno , Ratones , Animales , Peróxido de Hidrógeno/metabolismo , Insuficiencia Cardíaca/etiología , Miocitos Cardíacos/metabolismo , Ubiquitinación , Metiltransferasas/genética
12.
Signal Transduct Target Ther ; 8(1): 121, 2023 03 27.
Artículo en Inglés | MEDLINE | ID: mdl-36967385

RESUMEN

Heart failure (HF) patients in general have a higher risk of developing cancer. Several animal studies have indicated that cardiac remodeling and HF remarkably accelerate tumor progression, highlighting a cause-and-effect relationship between these two disease entities. Targeting ferroptosis, a prevailing form of non-apoptotic cell death, has been considered a promising therapeutic strategy for human cancers. Exosomes critically contribute to proximal and distant organ-organ communications and play crucial roles in regulating diseases in a paracrine manner. However, whether exosomes control the sensitivity of cancer to ferroptosis via regulating the cardiomyocyte-tumor cell crosstalk in ischemic HF has not yet been explored. Here, we demonstrate that myocardial infarction (MI) decreased the sensitivity of cancer cells to the canonical ferroptosis activator erastin or imidazole ketone erastin in a mouse model of xenograft tumor. Post-MI plasma exosomes potently blunted the sensitivity of tumor cells to ferroptosis inducers both in vitro in mouse Lewis lung carcinoma cell line LLC and osteosarcoma cell line K7M2 and in vivo with xenograft tumorigenesis model. The expression of miR-22-3p in cardiomyocytes and plasma-exosomes was significantly upregulated in the failing hearts of mice with chronic MI and of HF patients as well. Incubation of tumor cells with the exosomes isolated from post-MI mouse plasma or overexpression of miR-22-3p alone abrogated erastin-induced ferroptotic cell death in vitro. Cardiomyocyte-enriched miR-22-3p was packaged in exosomes and transferred into tumor cells. Inhibition of cardiomyocyte-specific miR-22-3p by AAV9 sponge increased the sensitivity of cancer cells to ferroptosis. ACSL4, a pro-ferroptotic gene, was experimentally established as a target of miR-22-3p in tumor cells. Taken together, our findings uncovered for the first time that MI suppresses erastin-induced ferroptosis through releasing miR-22-3p-enriched exosomes derived from cardiomyocytes. Therefore, targeting exosome-mediated cardiomyocyte/tumor pathological communication may offer a novel approach for the ferroptosis-based antitumor therapy.


Asunto(s)
Exosomas , Ferroptosis , Insuficiencia Cardíaca , MicroARNs , Infarto del Miocardio , Neoplasias , Humanos , Ratones , Animales , Miocitos Cardíacos/metabolismo , MicroARNs/genética , MicroARNs/metabolismo , Ferroptosis/genética , Exosomas/metabolismo , Infarto del Miocardio/genética , Neoplasias/metabolismo , Insuficiencia Cardíaca/genética , Insuficiencia Cardíaca/patología
13.
ACS Appl Mater Interfaces ; 15(8): 10383-10397, 2023 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-36800210

RESUMEN

In recent years, sunscreens' adverse impacts on the environment and biology have gained wide attention. The improvement of sunscreen safety has become one of the major priorities in skin photoprotection research. It is an effective strategy to develop bionic photoprotective materials by simulating the photoprotective mechanism existing in nature. Inspired by the photoprotective mechanisms of skin and plant leaves, the bionic photoprotective material CS-SA-PDA nanosheet was developed using the free radical grafting method and Michael addition, with natural melanin analogue polydopamine (PDA) nanoparticles and plant sunscreen molecular sinapic acid (SA) as sun protection factors and natural polymer chitosan (CS) as the connecting arm. The results show that CS-SA-PDA can effectively shield UVB and UVA due to the possible synergistic effect between PDA and SA. The introduction of polymer CS significantly improved the photostability of SA and reduced the skin permeability of PDA nanoparticles. The CS-SA-PDA nanosheet can also effectively scavenge photoinduced free radicals. Furthermore, in vivo toxicity and anti-UV evaluations confirm that CS-SA-PDA has no skin irritation and is excellent against skin photodamage, which makes it an ideal skin photoprotective material.


Asunto(s)
Protectores Solares , Rayos Ultravioleta , Protectores Solares/farmacología , Rayos Ultravioleta/efectos adversos , Factor de Protección Solar , Estrés Oxidativo , Radicales Libres , Polímeros
14.
Nanoscale ; 15(4): 1860-1868, 2023 Jan 27.
Artículo en Inglés | MEDLINE | ID: mdl-36602176

RESUMEN

In this work, we propose a silicene-based lateral resonant tunneling device by placing silicene under the superlattices interlaced, arranged by ferromagnetic gates and electric gates. Its ballistic transport properties are calculated by the transfer matrix method. Combined with the unique electrically tuned energy gap of silicene, its magnetoresistance (MR) can be exaggeratedly modulated over a wide range by applying electrostatic potential and the on-site potential difference. It is interestingly found that there is a quasi-periodic oscillation of the MR in silicene-based superlattice devices from the quantum resonant confinement of the band splitting by the electrostatic field. Moreover, the peak of the MR in a single-period structure can reach more than 104, while the peak of the MR in an interlaced alternating magnetic-electric silicene superlattice can reach more than 1017, which is one of the best-reported values. This may originate from the enhancement effect of the wave vector filtering by the controlled field. Our studies indicate that the silicene superlattices alternately arranged by the ferromagnetic gate and electric gate not only have giant MR (GMR) properties, but also exhibit the periodic oscillation characteristics of MR in which electric gates can be modulated. Therefore, this work provides a more flexible strategy for the construction of silicene-based nanoelectronic devices.

15.
J Org Chem ; 88(1): 189-197, 2023 01 06.
Artículo en Inglés | MEDLINE | ID: mdl-36548942

RESUMEN

The diverse structures of DNA serve as potent chiral scaffolds for DNA-based asymmetric catalysis, yet in most cases tens to hundreds of nucleotides in DNA hybrid catalysts hinder the deep insight into their structure-activity relationship. Owing to the structural simplicity and design flexibility of nucleotides, nucleotide-based catalysts have been emerging as a promising way to obtain fine structural information and understand the catalytic mechanisms. Herein, we found that a cyclic dinucleotide of cyclic di-AMP (c-di-AMP) and 1,10-phenanthroline copper(II) nitrate (Cu(phen)(NO3)2) are assembled to a c-di-AMP-based catalyst (c-di-AMP/Cu(phen)(NO3)2), which could fast achieve enantioselective fluorination in water with 90-99% yields and up to 90% enantiomeric excess (ee). The host-guest interaction between c-di-AMP and Cu(phen)(NO3)2 has been proposed mainly in a supramolecular interaction mode as evidenced by spectroscopic techniques of ultraviolet-visible, fluorescence, circular dichroism, and nuclear magnetic resonance. Cu(phen)(NO3)2 tightly binds to c-di-AMP with a binding constant of 1.7 ± 0.3 × 105 M-1, and the assembly of c-di-AMP/Cu(phen)(NO3)2 shows a modest rate enhancement to carbon-fluorine bond formations as supported by kinetic studies.


Asunto(s)
Halogenación , Agua , Estereoisomerismo , Cinética , Cobre/química , Nucleótidos , ADN/química
16.
Front Hum Neurosci ; 17: 1303230, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-38188507

RESUMEN

Purpose: Presently, research concerning alterations in brain structure among individuals with attention deficit hyperactivity disorder (ADHD) predominantly focuses on entire brain volume and cortical thickness. In this study, we extend our examination to the cortical microstructure of male children with ADHD. To achieve this, we employ the gray-white matter tissue contrast (GWC) metric, allowing for an assessment of modifications in gray matter density and white matter microstructure. Furthermore, we explore the potential connection between GWC and the severity of disorder in male children by ADHD. Methods: We acquired 3DT1 sequences from the public ADHD-200 database. In this study, we conducted a comparative analysis between 43 male children diagnosed with ADHD and 50 age-matched male controls exhibiting typical development trajectories. Our investigation entailed assessing differences in GWC and cortical thickness. Additionally, we explored the potential correlation between GWC and the severity of ADHD. To delineate the cerebral landscape, each hemisphere was subdivided into 34 cortical regions using freesurfer 7.2.0. For quantification, GWC was computed by evaluating the intensity contrast of non-normalized T1 images above and below the gray-white matter interface. Results: Our findings unveiled elevated GWC within the bilateral lingual, bilateral insular, left transverse temporal, right parahippocampal and right pericalcarine regions in male children with ADHD when contrasted with their healthy counterparts. Moreover, the cortical thickness in the ADHD group no notable distinctions that of control group in all areas. Intriguingly, the GWC of left transverse temporal demonstrated a negative correlation with the extent of inattention experienced by male children with ADHD. Conclusion: Utilizing GWC as a metric facilitates a more comprehensive assessment of microstructural brain changes in children with ADHD. The fluctuations in GWC observed in specific brain regions might serve as a neural biomarker, illuminating structural modifications in male children grappling with ADHD. This perspective enriches our comprehension of white matter microstructure and cortical density in these children. Notably, the inverse correlation between the GWC of the left transverse temporal and inattention severity underscores the potential role of structural and functional anomalies within this region in ADHD progression. Enhancing our insight into ADHD-related brain changes holds significant promise in deciphering potential neuropathological mechanisms.

17.
Proc Natl Acad Sci U S A ; 119(45): e2211228119, 2022 11 08.
Artículo en Inglés | MEDLINE | ID: mdl-36322742

RESUMEN

Magnetic targeting is one of the most promising approaches for improving the targeting efficiency by which magnetic drug carriers are directed using external magnetic fields to reach their targets. As a natural magnetic nanoparticle (MNP) of biological origin, the magnetosome is a special "organelle" formed by biomineralization in magnetotactic bacteria (MTB) and is essential for MTB magnetic navigation to respond to geomagnetic fields. The magnetic targeting of magnetosomes, however, can be hindered by the aggregation and precipitation of magnetosomes in water and biological fluid environments due to the strong magnetic attraction between particles. In this study, we constructed a magnetosome-like nanoreactor by introducing MTB Mms6 protein into a reverse micelle system. MNPs synthesized by thermal decomposition exhibit the same crystal morphology and magnetism (high saturation magnetization and low coercivity) as natural magnetosomes but have a smaller particle size. The DSPE-mPEG-coated magnetosome-like MNPs exhibit good monodispersion, penetrating the lesion area of a tumor mouse model to achieve magnetic enrichment by an order of magnitude more than in the control groups, demonstrating great prospects for biomedical magnetic targeting applications.


Asunto(s)
Magnetosomas , Magnetospirillum , Nanopartículas , Neoplasias , Ratones , Animales , Proteínas Bacterianas/metabolismo , Magnetosomas/química , Bacterias Gramnegativas/metabolismo , Nanopartículas/química , Campos Magnéticos , Neoplasias/metabolismo , Magnetospirillum/metabolismo
18.
Front Neurosci ; 16: 878146, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35812226

RESUMEN

In electroencephalograph (EEG) emotion recognition research, obtaining high-level emotional features with more discriminative information has become the key to improving the classification performance. This study proposes a new end-to-end emotion recognition method based on brain connectivity (BC) features and domain adaptive residual convolutional network (short for BC-DA-RCNN), which could effectively extract the spatial connectivity information related to the emotional state of the human brain and introduce domain adaptation to achieve accurate emotion recognition within and across the subject's EEG signals. The BC information is represented by the global brain network connectivity matrix. The DA-RCNN is used to extract high-level emotional features between different dimensions of EEG signals, reduce the domain offset between different subjects, and strengthen the common features between different subjects. The experimental results on the large public DEAP data set show that the accuracy of the subject-dependent and subject-independent binary emotion classification in valence reaches 95.15 and 88.28%, respectively, which outperforms all the benchmark methods. The proposed method is proven to have lower complexity, better generalization ability, and domain robustness that help to lay a solid foundation for the development of high-performance affective brain-computer interface applications.

19.
J Mater Chem B ; 10(19): 3759-3769, 2022 05 18.
Artículo en Inglés | MEDLINE | ID: mdl-35467687

RESUMEN

The hydrophobicity and inertness of the polypropylene (PP) material surface usually lead to serious biofouling and bacterial infections, which hamper its potential application as a biomedical polymer. Many strategies have been developed to improve its antifouling or antibacterial properties, yet designing a surface to achieve both antifouling and antibacterial performances simultaneously remains a challenge. Herein, we construct a dual-function micropatterned PP surface with antifouling and antibacterial properties through plasma activation, photomask technology and ultraviolet light-induced graft polymerization. Based on the antifouling agent poly(2-methacryloyloxyethyl phosphate choline) (PMPC) and the antibacterial agent quaternized poly(N,N-dimethylamino)ethyl methacrylate (QPDMAEMA), two different micropatterning structures have been successfully prepared: PP-PMPC-QPDMAEMA in which QPDMAEMA is the micropattern and PMPC is the coating polymer, and PP-QPDMAEMA-PMPC in which PMPC is the micropattern and QPDMAEMA is the coating polymer. The composition, elemental distribution and surface morphology of PP-PMPC-QPDMAEMA and PP-QPDMAEMA-PMPC have been thoroughly characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), respectively. Compared with pristine PP, the two types of micropatterned PP films exhibit good surface hydrophilicity as characterized by water contact angle measurements. The results of anti-protein adsorption, platelet adhesion and antibacterial evaluation showed that PP-PMPC-QPDMAEMA and PP-QPDMAEMA-PMPC had good anti-protein adsorption properties, especially for lysozyme (Lyz). They can effectively prevent platelet adhesion, and the anti-platelet adhesion performance of PP-QPDMAEMA-PMPC is slightly better than that of the PP-PMPC-QPDMAEMA sample. The sterilization rate of S. aureus and E. coli is as high as 95% for the two types of micropatterned PP films. Due to the rational design of micropatterns on the PP surface, the two classes of dual-functional PP materials realize both the resistance of protein and platelet adhesion, and the killing of bacteria at the same time. We anticipate that this work could provide a design strategy for the construction of multifunctional biomedical polymer materials.


Asunto(s)
Incrustaciones Biológicas , Polipropilenos , Antibacterianos/química , Antibacterianos/farmacología , Materiales Biocompatibles/química , Incrustaciones Biológicas/prevención & control , Escherichia coli , Polímeros/química , Polímeros/farmacología , Polipropilenos/química , Polipropilenos/farmacología , Espectroscopía Infrarroja por Transformada de Fourier , Staphylococcus aureus
20.
ACS Appl Mater Interfaces ; 14(14): 16197-16203, 2022 Apr 13.
Artículo en Inglés | MEDLINE | ID: mdl-35362955

RESUMEN

Open-framework structured materials such as Prussian blue analogues and sodium superionic conductor (NASICON) materials have been regarded as promising electrode candidates for aqueous batteries. These materials exhibit outstanding long cycle stability and high rate capacity retention, due to their high ion diffusive rate in the crystal and the stable structure maintenance in the electrochemical reaction process. Herein, an open-framework structured material [Ni(en)2]3[Fe(CN)6]2 (NienHCF) is prepared and first used as a cathode material for aqueous sodium- and potassium-ion batteries. The resultant material exhibits a high output potential and outstanding cycle performance (93.4% after 500 cycles at 1 A g-1) in K-ion batteries. Meanwhile, the electrochemical reaction mechanism is investigated. After coupling with the activated carbon anode, the K-ion full cell has 91.5% capacity retention at 5 A g-1 and retains 77.2% after 1000 cycles at 0.5 A g-1, exhibiting the potential as an electrode material for rechargeable aqueous K-ion and Na-ion batteries.

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