Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 18 de 18
Filtrar
1.
Nature ; 629(8012): 597-602, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38658762

RESUMEN

Hydroformylation is an industrial process for the production of aldehydes from alkenes1,2. Regioselective hydroformylation of propene to high-value n-butanal is particularly important, owing to a wide range of bulk applications of n-butanal in the manufacture of various necessities in human daily life3. Supported rhodium (Rh) hydroformylation catalysts, which often excel in catalyst recyclability, ease of separation and adaptability for continuous-flow processes, have been greatly exploited4. Nonetheless, they usually consist of rotationally flexible and sterically unconstrained Rh hydride dicarbonyl centres, only affording limited regioselectivity to n-butanal5-8. Here we show that proper encapsulation of Rh species comprising Rh(I)-gem-dicarbonyl centres within a MEL zeolite framework allows the breaking of the above model. The optimized catalyst exhibits more than 99% regioselectivity to n-butanal and more than 99% selectivity to aldehydes at a product formation turnover frequency (TOF) of 6,500 h-1, surpassing the performance of all heterogeneous and most homogeneous catalysts developed so far. Our comprehensive studies show that the zeolite framework can act as a scaffold to steer the reaction pathway of the intermediates confined in the space between the zeolite framework and Rh centres towards the exclusive formation of n-butanal.

2.
PLoS Pathog ; 20(9): e1012546, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-39316625

RESUMEN

Pseudorabies virus (PRV) infection causes systemic inflammatory responses and inflammatory damages in infected animals, which are associated with the activation of inflammasome and pyroptosis in infected tissues. Here, we identified a critical function of PRV non-structural protein UL4 that enhanced ASC-dependent inflammasome activation to promote pyroptosis. Whereas, the deficiency of viral UL4 was able to reduce ASC-dependent inflammasome activation and the occurrences of pyroptosis. Mechanistically, the 132-145 aa of UL4 permitted its translocation from the nucleus to the cytoplasm to interact with cytoplasmic ASC to promote the activation of NLRP3 and AIM2 inflammasome. Further research showed that UL4 promoted the phosphorylation levels of SYK and JNK to enhance the ASC phosphorylation, which led to the increase of ASC oligomerization, thus promoting the activation of NLRP3 and AIM2 inflammasome and enhanced GSDMD-mediated pyroptosis. In vivo experiments further showed that PRV UL4 (132DVAADAAAEAAAAE145) mutated strain (PRV-UL4mut) infection did not lead to a significant decrease in viral titers at 12 h. p. i, but it induced lower levels of IL-1ß, IL-18, and GSDMD-NT, which led to an alleviated inflammatory infiltration and pathological damage in the lungs and brains, and a lower death rate compared with wild-type PRV strain infection. Taken together, our findings unravel that UL4 is an important viral regulator to manipulate the inflammasome signaling and pyroptosis of host cells to promote the pathogenicity of PRV, which might be further exploited as a new target for live attenuated vaccines or therapeutic strategies against pseudorabies in the future.


Asunto(s)
Proteínas Adaptadoras de Señalización CARD , Herpesvirus Suido 1 , Inflamasomas , Inflamación , Seudorrabia , Piroptosis , Animales , Inflamasomas/metabolismo , Inflamasomas/inmunología , Ratones , Herpesvirus Suido 1/inmunología , Inflamación/metabolismo , Seudorrabia/virología , Seudorrabia/metabolismo , Seudorrabia/inmunología , Seudorrabia/patología , Proteínas Adaptadoras de Señalización CARD/metabolismo , Proteínas Virales/metabolismo , Proteínas Virales/genética , Ratones Endogámicos C57BL
3.
Sensors (Basel) ; 24(3)2024 Jan 29.
Artículo en Inglés | MEDLINE | ID: mdl-38339596

RESUMEN

Composite materials are frequently exposed to external factors during their operational service, resulting in internal structural damage which subsequently impacts their structural performance. This paper employs ferromagnetic materials for their sensitivity to magnetic field strength. By detecting variations in the magnetic field within the embedded ferromagnetic microwires of composite materials, the aim is to indirectly assess the health status of the composite materials. Firstly, a theoretical numerical model for magnetic field intensity at the crack site was established. Subsequently, a finite element model was employed to analyze the variations in the magnetic characteristics of ferromagnetic microwires at the crack site. Under different parameter conditions, the patterns of magnetic signals at the crack site were determined. The results indicate that with an increase in the angle between the external magnetic field and the crack, the fitted curve of the magnetic signal shows a linear increase. The distance between the peak and valley of the radial magnetic signal in the axial direction decreases, and the axial magnetic signal transitions from double-peak to single-peak. With the increase in crack depth, the fitted curve of the magnetic signal shows a linear increase, and the magnetic signal at the crack tip also exhibits a linear increase. An increase in crack width leads to a non-linear decrease in the fitted curve of the magnetic signal, and after reaching a certain width, the magnetic signal stabilizes. For two identical cracks at different distances, the magnetic signal exhibits a transition from a complete pattern to two complete patterns. With the increase in the external magnetic field, the magnetic signal shows a completely regular linear increase. By analyzing and calculating the variations in magnetic signals, the patterns of magnetic characteristics under the damaged state of ferromagnetic microwires were obtained. This serves as a basis for assessing whether they can continue in service and for evaluating the overall health status of composite materials.

4.
Molecules ; 29(5)2024 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-38474676

RESUMEN

An efficient dearomative (3 + 2) cycloaddition of para-quinamines and 2-nitrobenzofurans has been developed. This reaction proceeds smoothly under mild conditions and affords a series of benzofuro[3,2-b]indol-3-one derivatives in good to excellent yields (up to 98%) with perfect diastereoselectivities (all cases > 20:1 dr). The scale-up synthesis and versatile derivatizations demonstrate the potential synthetic application of the protocol. A plausible reaction mechanism is also proposed to account for the observed reaction process. This work represents the first instance of the N-triggered dearomative (3 + 2) cycloaddition of 2-nitrobenzofurans.

5.
Org Biomol Chem ; 21(7): 1373-1378, 2023 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-36723148

RESUMEN

A formal [4 + 2] cycloaddition of 3-nitroindoles with ortho-aminophenyl p-quinone methides via a dearomatization process was developed. This method provides a facile approach for preparing tetrahydro-5H-indolo[2,3-b]quinolones with good results. With the bifunctional Cinchona alkaloid-squaramide as the catalyst, the asymmetric version of the reaction successfully afforded the corresponding chiral products with moderate to good enantioselectivities. This work represents the first dearomative cycloaddition of electron-deficient heteroarenes triggered by aza-Michael addition from p-QMs.

6.
Molecules ; 28(20)2023 Oct 19.
Artículo en Inglés | MEDLINE | ID: mdl-37894659

RESUMEN

Exploring the properties of magnetic metal on the semiconductor surface is of great significance for the application of magnetic recording materials. Herein, DFT calculations are carried out to explore the properties of the iron-silicon interface structures (nFe/DASF) formed by depositing n Fe atoms on the reconstructed Si(111)-(7×7) surface (DASF). The stable nFe/DASF structures are studied in the cases of the adsorption and permeation of Fe atoms on the DASF. In both cases, Fe atoms are not very dispersed and prefer binding with Si atoms rather than the adsorbed Fe atoms, because the Fe-Si interaction is stronger than the Fe-Fe interaction. As the n value increases, the average binding energy (Eb_ave) of Fe generally firstly becomes more negative and then becomes less negative, with the presence of a 7Fe wheel as a stable geometry on the upmost surface. The presence of the 7Fe wheel is attributed to the enhanced Fe-Si interaction in this wheel compared to other geometries. CO adsorption occurs at the central Fe site of the 7Fe wheel which is greatly influenced by the surrounding Si atoms but is little influenced by the additional Fe atoms in the interlayer.

7.
Molecules ; 28(23)2023 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-38067627

RESUMEN

α-Substituted-7-azaindoline amides and α,ß-unsaturated 7-azaindoline amides have emerged as new versatile synthons for various metal-catalyzed and organic-catalyzed asymmetric reactions, which have attracted much attention from chemists. In this review, the progress of research on 7-azaindoline amides in the asymmetric aldol reaction, the Mannich reaction, the conjugate addition, the 1,3-dipole cycloaddition, the Michael/aldol cascade reaction, aminomethylation and the Michael addition-initiated ring-closure reaction is discussed. The α-substituted-7-azaindoline amides, as nucleophiles, are classified according to the type of α-substituted group, whereas the α,ß-unsaturated 7-azaindoline amides, as electrophiles, are classified according to the type of reaction.

8.
Molecules ; 28(7)2023 Mar 29.
Artículo en Inglés | MEDLINE | ID: mdl-37049822

RESUMEN

Heteroarene 1, n-zwitterions are powerful and versatile building blocks in the construction of heterocycles and have received increasing attention in recent years. In particular, pyridinium and quinolinium 1,4-zwitterions have been widely studied and used in a variety of cyclization reactions due to their air stability, ease of use, and high efficiency. Sulfur- and nitrogen-based pyridinium and quinolinium 1,4-zwitterions, types of emerging heteroatom-containing synthons, have attracted much attention from chemists. These 1,4-zwitterions, which contain multiple reaction sites, have been successfully used in the synthesis of three- to eight-membered cyclic compounds over the last decade. In this review, we present the exciting progress made in the field of cyclization reactions of sulfur- and nitrogen-based pyridinium and quinolinium 1,4-zwitterions. Moreover, the mechanistic insights, the transition states, some synthetic applications, and the challenges and opportunities are also discussed. We hope to provide an overview for synthetic chemists who are interested in the heterocycle synthesis from cyclization reaction with pyridinium and quinolinium 1,4-zwitterions pyridinium and quinolinium 1,4-zwitterions.

9.
Phys Chem Chem Phys ; 24(17): 10420-10438, 2022 May 04.
Artículo en Inglés | MEDLINE | ID: mdl-35441637

RESUMEN

A single-atom alloy (SAA) consisting of an abundant metal host and a precious metal guest is a promising catalyst to reduce the cost without a loss of activity. DFT calculations of Ni- and Cu-based alloys nX/M(111) (X = Cu, Ag, or Au for M = Ni; X = Ni, Pd, or Pt for M = Cu; n = 1-4) reveal that a phase-separated alloy (PSA) is produced by Cu atoms with Ni(111) but an SAA is produced by Au atoms with Ni(111) and Pd and Pt atoms with Cu(111). In the Ni(111)-based Ag alloy and Cu(111)-based Ni alloy, the relative stabilities of the SAA and PSA depend on coverages of Ag on Ni(111) and Ni on Cu(111). The interaction energy (Eint) between the Xn cluster and M(111) host is larger than that between one X atom and the M(111) host, because the Xn cluster forms more bonding interactions with the M(111) host than does one X atom. When going from one X atom to the X4 cluster, the Eint values of Au and Pt clusters respectively with Ni(111) and Cu(111) increase to a lesser extent than those of Cu and Ni clusters respectively with Ni(111) and Cu(111). Consequently, Au and Pt atoms tend to form SAAs respectively with Ni(111) and Cu(111) hosts compared to Cu and Ni atoms. This trend in the Eint value is determined by the valence orbital energies of the X atom and the Xn cluster. Cu atoms in nCu/Ni(111) have a slightly positive charge but Ag atoms in nAg/Ni(111), Au atoms in nAu/Ni(111), and Ni, Pd, and Pt atoms in nX/Cu(111) (X = Ni, Pd, or Pt) have a negative charge. The negative charge increases in the order Ag < Au in nX/Ni(111) and Ni < Pd < Pt in nX/Cu(111). The Fermi level decreases in energy in the order nCu/Ni(111) ≥ Ni(111) > nAg/Ni(111) > nAu/Ni(111) and Cu(111) ≥ nNi/Cu(111) > nPd/Cu(111) > nPt/Cu(111). The d valence band center decreases in energy in almost the same order. The CO adsorption energy decreases in the order Ni(111) ∼ nCu/Ni(111) > nAg/Ni(111) ∼ nAu/Ni(111) and Cu(111) > nNi/Cu(111) > nPd/Cu(111) > nPt/Cu(111). These properties are explained based on the electronic structures.

10.
Chemphyschem ; 22(13): 1287-1301, 2021 Jul 02.
Artículo en Inglés | MEDLINE | ID: mdl-33844400

RESUMEN

Zeolite-supported catalysts have been widely used in the field of heterogeneous catalysis. Atomic-scale governing the metal or acid sites on zeolites still encounters great challenge in controllable synthesis and developing of novel catalysts. Atomic layer deposition (ALD), owing to its unique character of self-limiting surface reactions, becomes one of the most promising and controllable strategies to tailor the metallic deposition sites in atomic scale precisely. In this review, we present a comprehensive summary and viewpoint of recent research in designing and engineering the structural of zeolite-based catalysts via ALD method. A prior focus is laid on the deposition of metals on the zeolites with emphasis on the isolated states of metals, followed by introducing the selected metals into channels of zeolites associates with identifying the location of metals in and/or out of the channels. Subsequently, detailed analysis of tailoring the acid sites of different zeolites is provided. Assisted synthesis of zeolite and the regioselective deposition of metal on special sites to modify the structures of zeolites are also critically discussed. We further summarize the challenges of ALD with respect to engineering the active sites in heterogeneous zeolite-based catalysts and provide the perspectives on the development in this field.

11.
Org Lett ; 2024 Feb 22.
Artículo en Inglés | MEDLINE | ID: mdl-38385527

RESUMEN

The first direct catalytic asymmetric Mannich reaction of 2-alkylazaarenes and ketimines was realized with a chiral Cu-bis(oxazoline) complex as the catalyst. The asymmetric addition of 2-alkylpyridines to isatin-derived ketimines proceeded smoothly to afford α,ß-functionalized 2-substituted pyridines bearing 3-amino-3,3-disubstituted oxindole motifs with excellent results (≤99% yield, 99:1 dr, and 98% ee). The catalytic system was also extended to 2-alkylbenzothiazoles as nucleophiles for the asymmetric Mannich reaction of ketimines.

12.
Vet Microbiol ; 284: 109826, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37421928

RESUMEN

Pseudorabies virus (PRV) preferably invades neural tissue and various organs, whereupon may result in multisystemic lesions. Pyroptosis mediated by proteolytic cleavage of gasdermin D (GSDMD) by inflammatory caspases (caspase-1/4/5/11), is closely associated with the activation of inflammasomes, a multiprotein proinflammatory complex. However, further studies on the mechanisms regarding PRV-induced pyroptosis in its natural host are required. Herein, it is demonstrated that PRV infection triggered GSDMD- not GSDME-mediated pyroptosis in porcine alveolar macrophage cells, resulting in increased secretion of IL-1ß and LDH. During this process, caspase-1 was activated and participated in the cleaving of GSDMD. Interestingly, we found that the viral replication process or protein production is required to induce pyroptotic cell death. Also, our findings showed that PRV triggered NLRP3 inflammasome activation, which was associated with the production of reactive oxygen species (ROS) and potassium efflux. In addition to the NLRP3 inflammasome, the IFI16 inflammasome was also activated. Importantly, the NLRP3- and IFI16- inflammasomes were both involved in pyroptosis during PRV infection. Finally, we observed that the cleaved GSDMD, activated caspase-1, increased IFI16 levels, and elevated NLRP3 protein in PRV-infected tissues (brain and lung), supporting the occurrence of pyroptosis and the activation of NLRP3- and IFI16- inflammasome in PRV-infected pigs. This research advances our understanding of the PRV-mediated inflammatory response and cell death pathways, providing a deeper knowledge of effective treatments for pseudorabies.


Asunto(s)
Herpesvirus Suido 1 , Inflamasomas , Animales , Porcinos , Inflamasomas/metabolismo , Proteína con Dominio Pirina 3 de la Familia NLR/genética , Proteína con Dominio Pirina 3 de la Familia NLR/metabolismo , Piroptosis/fisiología , Herpesvirus Suido 1/metabolismo , Caspasas , Caspasa 1/metabolismo
13.
Chem Commun (Camb) ; 59(49): 7483-7505, 2023 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-37222562

RESUMEN

Copper-catalyzed decarboxylative reactions of propargylic cyclic carbonates/carbamates enable the efficient construction of widely available skeletons such as allenes, ethynyl-containing heterocycles, and tetrasubstituted stereogenic carbon centers. As an emerging field, these strategies have gained great attention and shown significant progress due to the presence of multiple electrophilic and nucleophilic reaction sites of propargylic cyclic carbonates/carbamates, as well as the distinct advantages of copper catalysis such as higher selectivity, low cost, and mild reaction conditions. In this review, the achievements in copper-catalyzed decarboxylative reactions of propargylic cyclic carbonates/carbamates are addressed. Mechanistic insights, synthetic applications, and their limitations are discussed. The challenges and opportunities of this field are also outlined.


Asunto(s)
Carbamatos , Cobre , Carbonatos , Carbono , Catálisis
14.
Org Lett ; 25(8): 1274-1279, 2023 Mar 03.
Artículo en Inglés | MEDLINE | ID: mdl-36800376

RESUMEN

A copper-catalyzed diastereo- and enantioselective decarboxylative [3 + 2] cyclization reaction of alkyne-substituted cyclic carbamates with azlactones has been established. A range of optically pure γ-butyrolactams bearing two vicinal tetrasubstituted carbon stereocenters were obtained in high yields with good to excellent stereoselectivities (up to 99% yield, 99:1 dr, and 99% ee). This is the first example of asymmetric synthesis γ-butyrolactams containing sterically congested vicinal tetrasubstituted stereocenters via a decarboxylative cyclization pathway.

15.
Org Lett ; 25(51): 9191-9196, 2023 Dec 29.
Artículo en Inglés | MEDLINE | ID: mdl-38114417

RESUMEN

Herein, we report an unprecedented implementation of 3-halooxindoles as C-C-O three-atom components for (3+3) cycloaddition with pyridinium 1,4-zwitterionic thiolates, affording structurally diverse indolenine-fused 2H-1,4-oxathiines in moderate to high yields. A combined experimental and computational mechanistic study suggests that the reaction proceeds through addition of a S conjugate to the o-azaxylylene intermediate, followed by O-Michael addition and a sequential retro-Michael addition/pyridine extrusion pathway.

16.
Science ; 375(6585): 1188-1191, 2022 03 11.
Artículo en Inglés | MEDLINE | ID: mdl-35271314

RESUMEN

Polyethylene production through catalytic ethylene polymerization is one of the most common processes in the chemical industry. The popular Cossee-Arlman mechanism hypothesizes that the ethylene be directly inserted into the metal-carbon bond during chain growth, which has been awaiting microscopic and spatiotemporal experimental confirmation. Here, we report an in situ visualization of ethylene polymerization by scanning tunneling microscopy on a carburized iron single-crystal surface. We observed that ethylene polymerization proceeds on a specific triangular iron site at the boundary between two carbide domains. Without an activator, an intermediate, attributed to surface-anchored ethylidene (CHCH3), serves as the chain initiator (self-initiation), which subsequently grows by ethylene insertion. Our finding provides direct experimental evidence of the ethylene polymerization pathway at the molecular level.

17.
Sci Prog ; 104(1): 368504211003385, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33749415

RESUMEN

Fixed beam structures are widely used in engineering, and a common problem is determining the load conditions of these structures resulting from impact loads. In this study, a method for accurately identifying the location and magnitude of the load causing plastic deformation of a fixed beam using a backpropagation artificial neural network (BP-ANN). First, a load of known location and magnitude is applied to the finite element model of a fixed beam to create plastic deformation, and a polynomial expression is used to fit the resulting deformed shape. A basic data set was established through this method for a series of calculations, and it consists of the location and magnitude of the applied load and polynomial coefficients. Then, a BP-ANN model for expanding the sample data is established and the sample set is expanded to solve the common problem of insufficient samples. Finally, using the extended sample set as training data, the coefficients of the polynomial function describing the plastic deformation of the fixed beam are used as input data, the position and magnitude of the load are used as output data, a BP-ANN prediction model is established. The prediction results are compared with the results of finite element analysis to verify the effectiveness of the method.


Asunto(s)
Redes Neurales de la Computación , Plásticos , Algoritmos , Análisis de Elementos Finitos
18.
Artículo en Inglés | MEDLINE | ID: mdl-27085169

RESUMEN

A new aromatic criterion is presented to determine the aromatic degree of the high symmetric molecules. Group theory is used to explain the correlation between the aromatic degree and the value of Ring Stretching Vibration Raman Spectroscopic Frequency (RSVRSF). The calculations of the geometrical optimization, nucleus-independent chemical shifts (NICS) and values of the Raman Spectroscopy for the aromatic molecules-LnHn (L=C, Si, Ge, n=3, 5-8) were performed using the Density Functional Theory (DFT) Method, as well as the correlations between the values of their RSVRSF and NICS values by Statistic Package for Social Science (SPSS17.0). There are high positive correlations between the theoretical calculated the NICS values and the value of the RSVRSF (A1g/A1') of the LnHn (L=C, Si, Ge, n=3, 5-8). The bigger the aromatic degree, the bigger the RSVRSF is. The value of the RSVRSF is a new probe of aromaticity. Expectedly, it is predicted that the experimental determination of the aromatic degree can be achieved by the determination of the ring stretching vibration (A1g/A1') Raman spectrum frequencies for the aromatic target molecules.

SELECCIÓN DE REFERENCIAS
DETALLE DE LA BÚSQUEDA