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1.
Cell ; 185(8): 1325-1345.e22, 2022 04 14.
Artículo en Inglés | MEDLINE | ID: mdl-35366418

RESUMEN

Protein aggregation is a hallmark of multiple human pathologies. Autophagy selectively degrades protein aggregates via aggrephagy. How selectivity is achieved has been elusive. Here, we identify the chaperonin subunit CCT2 as an autophagy receptor regulating the clearance of aggregation-prone proteins in the cell and the mouse brain. CCT2 associates with aggregation-prone proteins independent of cargo ubiquitination and interacts with autophagosome marker ATG8s through a non-classical VLIR motif. In addition, CCT2 regulates aggrephagy independently of the ubiquitin-binding receptors (P62, NBR1, and TAX1BP1) or chaperone-mediated autophagy. Unlike P62, NBR1, and TAX1BP1, which facilitate the clearance of protein condensates with liquidity, CCT2 specifically promotes the autophagic degradation of protein aggregates with little liquidity (solid aggregates). Furthermore, aggregation-prone protein accumulation induces the functional switch of CCT2 from a chaperone subunit to an autophagy receptor by promoting CCT2 monomer formation, which exposes the VLIR to ATG8s interaction and, therefore, enables the autophagic function.


Asunto(s)
Chaperonina con TCP-1 , Macroautofagia , Agregado de Proteínas , Animales , Ratones , Proteínas Reguladoras de la Apoptosis/metabolismo , Autofagia/fisiología , Proteínas Portadoras/metabolismo , Chaperonina con TCP-1/metabolismo , Proteína Sequestosoma-1/metabolismo
2.
Nature ; 617(7959): 118-124, 2023 05.
Artículo en Inglés | MEDLINE | ID: mdl-37100915

RESUMEN

Modern green revolution varieties of wheat (Triticum aestivum L.) confer semi-dwarf and lodging-resistant plant architecture owing to the Reduced height-B1b (Rht-B1b) and Rht-D1b alleles1. However, both Rht-B1b and Rht-D1b are gain-of-function mutant alleles encoding gibberellin signalling repressors that stably repress plant growth and negatively affect nitrogen-use efficiency and grain filling2-5. Therefore, the green revolution varieties of wheat harbouring Rht-B1b or Rht-D1b usually produce smaller grain and require higher nitrogen fertilizer inputs to maintain their grain yields. Here we describe a strategy to design semi-dwarf wheat varieties without the need for Rht-B1b or Rht-D1b alleles. We discovered that absence of Rht-B1 and ZnF-B (encoding a RING-type E3 ligase) through a natural deletion of a haploblock of about 500 kilobases shaped semi-dwarf plants with more compact plant architecture and substantially improved grain yield (up to 15.2%) in field trials. Further genetic analysis confirmed that the deletion of ZnF-B induced the semi-dwarf trait in the absence of the Rht-B1b and Rht-D1b alleles through attenuating brassinosteroid (BR) perception. ZnF acts as a BR signalling activator to facilitate proteasomal destruction of the BR signalling repressor BRI1 kinase inhibitor 1 (TaBKI1), and loss of ZnF stabilizes TaBKI1 to block BR signalling transduction. Our findings not only identified a pivotal BR signalling modulator but also provided a creative strategy to design high-yield semi-dwarf wheat varieties by manipulating the BR signal pathway to sustain wheat production.


Asunto(s)
Biomasa , Brasinoesteroides , Grano Comestible , Transducción de Señal , Triticum , Alelos , Brasinoesteroides/metabolismo , Grano Comestible/genética , Grano Comestible/crecimiento & desarrollo , Grano Comestible/metabolismo , Eliminación de Gen , Genes de Plantas , Giberelinas/metabolismo , Fenotipo , Triticum/clasificación , Triticum/genética , Triticum/crecimiento & desarrollo , Triticum/metabolismo , Proteínas de Plantas/genética , Productos Agrícolas/genética , Productos Agrícolas/crecimiento & desarrollo , Productos Agrícolas/metabolismo
3.
Genes Dev ; 33(1-2): 90-102, 2019 01 01.
Artículo en Inglés | MEDLINE | ID: mdl-30567997

RESUMEN

Piwi-interacting RNAs (piRNAs) engage Piwi proteins to suppress transposons and nonself nucleic acids and maintain genome integrity and are essential for fertility in a variety of organisms. In Caenorhabditis elegans, most piRNA precursors are transcribed from two genomic clusters that contain thousands of individual piRNA transcription units. While a few genes have been shown to be required for piRNA biogenesis, the mechanism of piRNA transcription remains elusive. Here we used functional proteomics approaches to identify an upstream sequence transcription complex (USTC) that is essential for piRNA biogenesis. The USTC contains piRNA silencing-defective 1 (PRDE-1), SNPC-4, twenty-one-U fouled-up 4 (TOFU-4), and TOFU-5. The USTC forms unique piRNA foci in germline nuclei and coats the piRNA cluster genomic loci. USTC factors associate with the Ruby motif just upstream of type I piRNA genes. USTC factors are also mutually dependent for binding to the piRNA clusters and forming the piRNA foci. Interestingly, USTC components bind differentially to piRNAs in the clusters and other noncoding RNA genes. These results reveal the USTC as a striking example of the repurposing of a general transcription factor complex to aid in genome defense against transposons.


Asunto(s)
Proteínas de Caenorhabditis elegans/metabolismo , Caenorhabditis elegans/genética , Caenorhabditis elegans/metabolismo , Regulación de la Expresión Génica/genética , ARN Interferente Pequeño/genética , Secuencias de Aminoácidos , Animales , Proteínas de Caenorhabditis elegans/genética , Genoma de los Helmintos/genética , Unión Proteica , Proteómica , ARN Interferente Pequeño/biosíntesis
4.
Nano Lett ; 24(6): 1951-1958, 2024 Feb 14.
Artículo en Inglés | MEDLINE | ID: mdl-38315061

RESUMEN

We show that a diffusive memristor with analogue switching characteristics can be achieved in a layer of gold nanoparticles (AuNPs) functionalized with charged self-assembled monolayers (deprotonated 11-mercaptoundecanoic acid). The nanoparticle core and the anchored stationary charges are jammed within the layer while the mobile counterions [N(CH3)4+] can respond to the electric field and spontaneously diffuse back to the initial positions upon removal of the field. This metal nanoparticle device is set-step free, energy consumption efficient, mechanically flexible, and analogous to bio-Ca2+ dynamics and has tunable conductance modulation capabilities at the counterion concentrations. The gradual resistive switching behavior enables us to implement several important synaptic functions such as potentiation/depression, spike voltage-dependent plasticity, spike duration-dependent plasticity, spike frequency-dependent plasticity, and paired-pulse facilitation. Finally, on the basis of the paired-pulse facilitation characteristics, the metal nanoparticle diffusive artificial synapse is used for edge extraction with exhibits excellent performance.

5.
Opt Express ; 32(7): 12200-12212, 2024 Mar 25.
Artículo en Inglés | MEDLINE | ID: mdl-38571050

RESUMEN

As an integral component of the laser interferometry measurement system, the tilt-to-length (TTL) coupling noise inside the telescope stands out as a critical noise factor that requires meticulous consideration. In the TianQin project, the non-geometric TTL-coupled noise inside the telescope should be less than 0.22 pm/Hz1/2. Additionally, the wavefront aberration RMS at the small pupil of the telescope needs to be better than 0.0065 λ. These requirements set for the telescope are exceptionally stringent. To address this challenge, this study aims to relax the wavefront aberration requirements by mitigating non-geometric TTL coupling noise, while ensuring the non-geometric TTL coupling noise remains below 0.22 pm/Hz1/2. By controlling the coupling aberration proportion, the wavefront aberration RMS at the small pupil of the telescope can be relaxed to 0.014 λ. Alternatively, optimizing the Gaussian beam waist radius can relax the wavefront aberration RMS to 0.016 λ. By simultaneously utilizing two optimization methods, the wavefront aberration at the small pupil of the telescope can be reduced to 0.033 λ, resulting in an impressive success rate of 91.15% in meeting the noise requirements.

6.
Opt Express ; 32(6): 9602-9609, 2024 Mar 11.
Artículo en Inglés | MEDLINE | ID: mdl-38571190

RESUMEN

The thin flyer is a small-scale flying object, which is well known as the core functional element of the initiator. Understanding how flyers perform has been a long-standing issue in detonator science. However, it remains a significant challenge to explore how the flyer is formed and functions in the barrel of the initiator via tabletop devices. In this study, we present dynamic and unprecedented images of flyer in barrel via high intensity short-pulse laser. Advanced radiography, coupled with a high-intensity picosecond laser X-ray source, has enabled the provision of state-of-the-art radiographs in a single-shot experiment for observing micron-scale flyer formation in a hollow cylinder in nanoseconds. The flyer was clearly visible in the barrel and was accelerated and restricted differently from that without the barrel. This first implementation of a tabletop X-ray source provided a new approach for capturing dynamic photographs of small-scale flying objects, which were previously reported to be accessible only via an X-ray phase-contrast imaging system at the advanced photon source. These efforts have led to a significant improvement of radiographic capability and a greater understanding of the mechanisms of "burst" of exploding foil initiators for this application.

7.
J Chem Inf Model ; 64(8): 3047-3058, 2024 Apr 22.
Artículo en Inglés | MEDLINE | ID: mdl-38520328

RESUMEN

Covalent drugs exhibit advantages in that noncovalent drugs cannot match, and covalent docking is an important method for screening covalent lead compounds. However, it is difficult for covalent docking to screen covalent compounds on a large scale because covalent docking requires determination of the covalent reaction type of the compound. Here, we propose to use deep learning of a lateral interactions spiking neural network to construct a covalent lead compound screening model to quickly screen covalent lead compounds. We used the 3CL protease (3CL Pro) of SARS-CoV-2 as the screen target and constructed two classification models based on LISNN to predict the covalent binding and inhibitory activity of compounds. The two classification models were trained on the covalent complex data set targeting cysteine (Cys) and the compound inhibitory activity data set targeting 3CL Pro, respected, with good prediction accuracy (ACC > 0.9). We then screened the screening compound library with 6 covalent binding screening models and 12 inhibitory activity screening models. We tested the inhibitory activity of the 32 compounds, and the best compound inhibited SARS-CoV-2 3CL Pro with an IC50 value of 369.5 nM. Further assay implied that dithiothreitol can affect the inhibitory activity of the compound to 3CL Pro, indicating that the compound may covalently bind 3CL Pro. The selectivity test showed that the compound had good target selectivity to 3CL Pro over cathepsin L. These correlation assays can prove the rationality of the covalent lead compound screening model. Finally, covalent docking was performed to demonstrate the binding conformation of the compound with 3CL Pro. The source code can be obtained from the GitHub repository (https://github.com/guzh970630/Screen_Covalent_Compound_by_LISNN).


Asunto(s)
Proteasas 3C de Coronavirus , Simulación del Acoplamiento Molecular , Redes Neurales de la Computación , SARS-CoV-2 , Proteasas 3C de Coronavirus/metabolismo , Proteasas 3C de Coronavirus/antagonistas & inhibidores , Proteasas 3C de Coronavirus/química , SARS-CoV-2/enzimología , SARS-CoV-2/efectos de los fármacos , Humanos , Descubrimiento de Drogas , Antivirales/farmacología , Antivirales/química , Antivirales/metabolismo , Inhibidores de Proteasas/farmacología , Inhibidores de Proteasas/química , Inhibidores de Proteasas/metabolismo , Tratamiento Farmacológico de COVID-19 , Aprendizaje Profundo , Unión Proteica , COVID-19/virología
8.
Nicotine Tob Res ; 26(6): 655-662, 2024 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-38157415

RESUMEN

INTRODUCTION: The prevalence of waterpipe tobacco smoking is increasing globally. Biomarkers of waterpipe tobacco smoke (WTS) exposure are less studied. AIMS AND METHODS: To identify the types of biomarkers of WTS exposure and estimate changes in biomarker concentrations pre- to post-WTS exposure. PubMed, Embase, Web of Science, CINAHL Plus, PsycINFO, and Cochrane Library were searched for studies up to April 24, 2023. The types of biomarkers were identified. Random-effects models were used to estimate changes in biomarker concentrations pre- to post-WTS exposure. RESULTS: Seventy-three studies involving 3755 participants exposed to WTS (49% male, mean age: 24.8 years) and 11 types of biomarkers of WTS exposure were identified. The biomarkers included tobacco alkaloids, expired carbon monoxide (eCO), carboxyhemoglobin (COHb), tobacco-specific nitrosamines, volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), heavy metals, unmetabolized VOCs, unmetabolized PAHs, furan metabolites, and heterocyclic aromatic amines. Compared with pre-WTS exposure, eCO (breath; mean difference [MD] 27.00 ppm; 95% confidence interval [CI]: 20.91 to 33.08), COHb (blood; MD 4.30%; 95%CI: 2.57 to 6.03), COHb (breath; MD 7.14%; 95%CI: 4.96 to 9.31), nicotine (blood; MD 8.23 ng/mL; 95%CI: 6.27 to 10.19), and cotinine (urine; MD 110.40 ng/mL; 95%CI: 46.26 to 174.54) significantly increased post-WTS exposure. CONCLUSIONS: Biomarkers of WTS exposure were systematically identified. The similarity between the biomarkers of WTS exposure and those of cigarette smoke and higher concentrations of some biomarkers post-WTS exposure underscore the need for further research on applying biomarkers in surveillance, interventions, and regulations to mitigate the harms of waterpipe tobacco smoking. IMPLICATIONS: This study provides the first comprehensive overview of biomarkers investigated and available for assessing WTS exposure and their concentration changes in the human body. Researchers can use biomarkers such as eCO, COHb, nicotine, and cotinine to measure the health risks associated with WTS exposure and objectively evaluate the effectiveness of public health interventions aimed at reducing waterpipe tobacco smoking. Public health policymaking can also be informed through increased biomarker concentrations following WTS exposure, to implement regulations and public health education campaigns on limiting or preventing waterpipe tobacco smoking.


Asunto(s)
Biomarcadores , Monóxido de Carbono , Tabaco para Pipas de Agua , Fumar en Pipa de Agua , Humanos , Monóxido de Carbono/análisis , Masculino , Contaminación por Humo de Tabaco/efectos adversos , Contaminación por Humo de Tabaco/análisis , Compuestos Orgánicos Volátiles/análisis , Femenino , Adulto , Adulto Joven , Carboxihemoglobina/análisis , Carboxihemoglobina/metabolismo
9.
J Nat Prod ; 87(4): 1103-1115, 2024 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-38600744

RESUMEN

Twelve new alkaloids, scolopenolines A-L (1-7, 9-11, 13, 14), along with six known analogues, were isolated from Scolopendra subspinipes mutilans, identified by analysis of spectroscopic data and quantum chemical and computational methods. Scolopenoline A (1), a unique guanidyl-containing C14 quinoline alkaloid, features a 6/6/5 ring backbone. Scolopenoline B (2) is a novel sulfonyl-containing heterodimer comprising quinoline and tyramine moieties. Scolopenoline G (7) presents a rare C12 quinoline skeleton with a 6/6/5 ring system. Alkaloids 1, 8, 10, and 15-18 display anti-inflammatory activity, while 10 and 16-18 also exhibit anti-renal-fibrosis activity. Drug affinity responsive target stability and RNA-interference assays show that Lamp2 might be a potentially important target protein of 16 for anti-renal-fibrosis activity.


Asunto(s)
Alcaloides , Animales Ponzoñosos , Quilópodos , Animales , Alcaloides/farmacología , Alcaloides/química , Alcaloides/aislamiento & purificación , Estructura Molecular , Artrópodos/química , Fibrosis/tratamiento farmacológico , Riñón/efectos de los fármacos , Quinolinas/farmacología , Quinolinas/química , Antiinflamatorios/farmacología , Antiinflamatorios/química , Humanos
10.
Bioorg Chem ; 144: 107169, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38330722

RESUMEN

Four undescribed compounds including one aromatic glucoside derivative, cordyceglycoside A (1), one new isoleucine derivative inner salt, cordycepisosalt A (2), a rare four-membered lactam, cinerealactam B (3), and one sesquiterpene derivative, cordycepsetp A (4), together with six known compounds were isolated from Cordyceps militaris. The structures including absolute configurations of these new compounds, were unambiguously elucidated by spectroscopic data analysis and single crystal X-ray diffraction. Biological evaluation of compounds 1-4 showed that 3 displays anti-renal fibrotic activities in TGF-ß1 induced NRK-52e cells. Furthermore, DARTS coupled with LC-MS/MS analysis was used to identify candidate target proteins for 3. Subsequently, C1qbp knockdown using siRNA allowed us to validate the target protein of 3.


Asunto(s)
Cordyceps , Cordyceps/química , Cordyceps/metabolismo , Cromatografía Liquida , Espectrometría de Masas en Tándem , Análisis Espectral , Fibrosis
11.
Appl Opt ; 63(7): 1815-1821, 2024 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-38437285

RESUMEN

The telescope is vital for accurate gravitational wave detection in the TianQin project. It must meet criteria like a geometric tilt-to-length (TTL) coupling noise c o e f f i c i e n t≤0.02√2n m/µr a d and wavefront R M S≤λ/30. Analyzing the pupil aberration's impact on geometric TTL noise, we devised an optimization method using the chief ray spot diagram's standard deviation. Implementing this in Zemax with a ZPL macro, we designed an optical system meeting TianQin's requirements. The system has a maximum geometric TTL noise coefficient of 0.0250 nm/µrad over the science FOV and a wavefront RMS of 0.0111λ, confirming the method's feasibility.

12.
Appl Opt ; 63(6): 1488-1494, 2024 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-38437360

RESUMEN

The optical path length stability of the off-axis four-reflection telescope is one of the key technical indicators for the TianQin gravitational wave detection system. In the MHz observation band, the telescope must exhibit an optical path length stability of 0.4p m/H z 1/2. As a feasible solution, the optical path length stability measurement of the off-axis four-reflection telescope based on the Pound-Drever-Hall (PDH) technique imposes stringent requirements on the alignment of the off-axis resonant cavity (ORC). Taking the off-axis two-reflection prototype as the research object, we propose a Monte Carlo analysis-based method for ORC alignment precision analysis. By considering misalignment as an intermediate function, we establish a relationship between the coupling efficiency of the ORC and the wavefront aberration of the telescope. The research results show that by considering the combined effects of multiple misalignment couplings of the primary and secondary mirrors, when the detected telescope wavefront aberration is better than 0.068λ (λ=1064n m) with a probability of 98%, the ORC coupling efficiency can achieve greater than 40% with a probability of 97.13%, which can be used as the main reference indicator for system misalignment analysis. This method simplifies the alignment difficulty of the target under test and can provide alignment reference for subsequent resonant cavities with internal off-axis telescopes.

13.
Sensors (Basel) ; 24(9)2024 May 02.
Artículo en Inglés | MEDLINE | ID: mdl-38733013

RESUMEN

During the operation of space gravitational wave detectors, the constellation configuration formed by three satellites gradually deviates from the ideal 60° angle due to the periodic variations in orbits. To ensure the stability of inter-satellite laser links, active compensation of the breathing angle variation within the constellation plane is achieved by rotating the optical subassembly through the telescope pointing mechanism. This paper proposes a high-performance robust composite control method designed to enhance the robust stability, disturbance rejection, and tracking performance of the telescope pointing system. Specifically, based on the dynamic model of the telescope pointing mechanism and the disturbance noise model, an H∞ controller has been designed to ensure system stability and disturbance rejection capabilities. Meanwhile, employing the method of an H∞ norm optimized disturbance observer (HODOB) enhances the nonlinear friction rejection ability of the telescope pointing system. The simulation results indicate that, compared to the traditional disturbance observer (DOB) design, utilizing the HODOB method can enhance the tracking accuracy and pointing stability of the telescope pointing system by an order of magnitude. Furthermore, the proposed composite control method improves the overall system performance, ensuring that the stability of the telescope pointing system meets the 10 nrad/Hz1/2 @0.1 mHz~1 Hz requirement specified for the TianQin mission.

14.
J Environ Manage ; 364: 121423, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38870788

RESUMEN

Unlike most previous studies considering the yields on green bonds versus conventional bonds or the hedging ability of green bonds against downside market risk, the main purpose of this paper is to paper examine the short-term response of green and conventional bonds to the Russia-Ukraine conflict shock and the US Federal monetary policy tightening. Using daily data from August 3, 2021 to March 29, 2022, this paper conducts an event-based study (Cumulative Abnormal Returns, CAR) and then applies a hedging analysis in the context of increasing geopolitical risk and financial stress. The analysis reveals that green bonds exhibit a stronger reaction to the Russia-Ukraine conflict and the US Federal rate hike than conventional, municipal, and treasury bonds in different time frames. Compared to conventional, municipal, and treasury bonds, green bonds offer lower negative CAR responses during the event window and the [-5, +5] period, suggesting a rigidity feature. The dynamic correlation and hedging analysis indicate that green bonds, unlike the other bonds indices, have a negative dynamic correlation with both geopolitical risks and financial stress, implying a hedging ability around the conflict shock and the Federal tightening cycle. These findings enrich the existing literature on green bonds, offering a wide range of applications for investment managers and policymakers.

15.
Molecules ; 29(3)2024 Feb 04.
Artículo en Inglés | MEDLINE | ID: mdl-38338459

RESUMEN

Recycled crumb rubber (RCR) is considered a reliable asphalt modifier and a solution to the problem of scrap tyre recycling. RCR-modified asphalt (RCRMA) typically has good low-temperature performance and storage stability. However, the pre-treatment of crumb rubber (CR) impairs its physical properties, resulting in poor high-temperature performance, which limits the industrial application of RCRMA. In this study, low-density polyethylene (LDPE) composite RCR was used to modify asphalt, and LDPE/RCR-composite-modified asphalt (L-RCRMA) was produced to compensate for the deficiencies in the high-temperature performance of RCRMA. The comprehensive physical properties of L-RCRMA were elucidated using tests such as the conventional properties, rotational viscosity, and rheological tests. The results showed that the incorporation of LDPE improved the high-temperature stability and rutting resistance of the asphalt, but an excessive amount of LDPE impaired the low-temperature performance and storage stability of L-RCRMA. Therefore, it is necessary to control the amount of LDPE to balance the performance of the asphalt. On this basis, we recommend a dosage of 20% for RCR and 1.5% for LDPE.

16.
Molecules ; 29(8)2024 Apr 10.
Artículo en Inglés | MEDLINE | ID: mdl-38675523

RESUMEN

Microelectromechanical systems (MEMS) gas sensors have numerous advantages such as compact size, low power consumption, ease of integration, etc., while encountering challenges in sensitivity and high resistance because of their low sintering temperature. This work utilizes the in situ growth of Zeolitic Imidazolate Framework-8 (ZIF-8) followed by its conversion to N-doped ZnO. The results obtained from scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicate that the in situ derivation of ZIF-8 facilitates the adhesion of ZnO particles, forming an island-like structure and significantly reducing the interfaces between these particles. Furthermore, powder X-ray diffraction (XRD) analysis, elemental mapping, and X-ray photoelectron spectroscopy (XPS) analysis confirm the conversion of ZIF-8 to ZnO, the successful incorporation of N atoms into the ZnO lattice, and the creation of more oxygen vacancies. The ZIF-8-derived N-doped ZnO/MEMS sensor (ZIF (3)-ZnO/MEMS) exhibits remarkable gas sensitivity for ethanol detection. At an operating temperature of 290 °C, it delivers a substantial response value of 80 towards 25 ppm ethanol, a 13-fold enhancement compared with pristine ZnO/MEMS sensors. The sensor also exhibits an ultra-low theoretical detection limit of 11.5 ppb to ethanol, showcasing its excellent selectivity. The enhanced performance is attributed to the incorporation of N-doped ZnO, which generates abundant oxygen vacancies on the sensor's surface, leading to enhanced interaction with ethanol molecules. Additionally, a substantial two-order-of-magnitude decrease in the resistance of the gas-sensitive film is observed. Overall, this study provides valuable insights into the design and fabrication strategies applicable to high-performance MEMS gas sensors in a broader range of gas sensing.

17.
Angew Chem Int Ed Engl ; : e202407575, 2024 Jun 20.
Artículo en Inglés | MEDLINE | ID: mdl-38899382

RESUMEN

Crown ethers (CEs), known for their exceptional host-guest complexation, offer potential as linkers in covalent organic frameworks (COFs) for enhanced performance in catalysis and host-guest binding. However, their highly flexible conformation and low symmetry limit the diversity of CE-derived COFs. Here, we introduce a novel C3-symmetrical azacrown ether (ACE) building block, tris(pyrido)[18]crown-6 (TPy18C6), for COF fabrication (ACE-COF-1 and ACE-COF-2) via reticular synthesis. This approach enables precise integration of CEs into COFs, enhancing Ni2+ ion immobilization while maintaining crystallinity. The resulting Ni2+-doped COFs (Ni@ACE-COF-1 and Ni@ACE-COF-2) exhibit high discharge capacity (up to 1.27 mAh·cm-2 at 8 mA·cm-2) and exceptional cycling stability (>1000 cycles) as cathode materials in aqueous alkaline nickel-zinc batteries. This study serves as an exemplar of the seamless integration of macrocyclic chemistry and reticular chemistry, laying the groundwork for extending the macrocyclic-synthon driven strategy to a diverse array of COF building blocks, ultimately yielding advanced materials tailored for specific applications.

18.
Angew Chem Int Ed Engl ; : e202408765, 2024 May 26.
Artículo en Inglés | MEDLINE | ID: mdl-38797705

RESUMEN

Despite the great research interest in two-dimensional metal nanowire networks (2D MNWNs) due to their large specific surface area and abundance of unsaturated coordination atoms, their controllable synthesis still remains a significant challenge. Herein, a microfluidics laminar flow-based approach is developed, enabling the facile preparation of large-scale 2D structures with diverse alloy compositions, such as PtBi, AuBi, PdBi, PtPdBi, and PtAuCu alloys. Remarkably, these 2D MNWNs can reach sizes up to submillimeter scale (~220 µm), which is significantly larger than the evolution from the 1D or 3D counterparts that typically measure only tens of nanometers. The PdBi 2D MNWNs affords the highest specific activity for formic acid (2669.1 mA mg-1) among current unsupported catalysts, which is 103.5 times higher than Pt-black, respectively. Furthermore, in situ Fourier transform infrared (FTIR) experiments provide comprehensive evidence that PdBi 2D MNWNs catalysts can effectively prevent CO* poisoning, resulting in exceptional activity and stability for the oxidation of formic acid.

19.
J Am Chem Soc ; 145(31): 17242-17252, 2023 Aug 09.
Artículo en Inglés | MEDLINE | ID: mdl-37499231

RESUMEN

Catalytic approaches to generate enantiospecific chiral centers are the major premise of modern organic chemistry. Heterogeneous catalysis is responsible for the vast majority of chemical transformations, yet the direct employment of chiral solid catalysts for asymmetric synthesis is mostly overlooked. Here, we demonstrated that a heterogeneous metal-halide perovskite nanocrystal (NC) catalyst is active for asymmetric organic synthesis under visible-light activation. Chiral 1-phenylethylamine (PEA)-hybridized perovskite PEA/CsPbBr3 NC photocatalysts exhibit an enantioselective (up to 99% enantiomer excess, ee) avenue to produce N-C axially chiral N-heterocycles, i.e., N-arylindoles from N-arylamine photo-oxidation. Mechanistic investigation indicated a discriminated prochiral binding of the N-arylamine substrates onto the chiral-NC surface with ca. -2.4 kcal/mol enantiodifferentiation. Our perovskite NC heterogeneous catalytic system not only demonstrates a promising strategy to address the long-term challenges in atroposelective pharmaceutical scaffold synthesis but also paves the road to directly employ chiral solids for asymmetric synthesis.

20.
J Am Chem Soc ; 145(16): 8860-8870, 2023 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-37070784

RESUMEN

The selective photoisomerization or photocyclization of stilbene to achieve value upgrade is of great significance in industry applications, yet it remains a challenge to accomplish both of them through a one-pot photocatalysis strategy under mild conditions. Here, a sevenfold interpenetrating 3D covalent organic framework (TPDT-COF) has been synthesized through covalent coupling between N,N,N,N-tetrakis(4-aminophenyl)-1,4-benzenediamine (light absorption and free radical generation) and 5,5'-(2,1,3-benzothiadiazole-4,7-diyl)bis[2-thiophenecarboxaldehyde] (catalytic center). The thus-obtained sevenfold interpenetrating structure presents a functional pore channel with a tunable photocatalytic ability and specific pore confinement effect that can be applied for selective stilbene photoisomerization and photocyclization. Noteworthily, it enables photogeneration of cis-stilbene or phenanthrene with >99% selectivity by simply changing the gas atmosphere under mild conditions (Ar, SeleCis. > 99%, SelePhen. < 1% and O2, SeleCis. < 1%, and SelePhen. > 99%). Theoretical calculations prove that different gas atmospheres possess varying influences on the energy barriers of reaction intermediates, and the pore confinement effect plays a synergistically catalytic role, thus inducing different product generation. This study might facilitate the exploration of porous crystalline materials in selective photoisomerization and photocyclization.

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