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1.
J Immunol ; 213(5): 730-742, 2024 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-38984862

RESUMEN

Teleost IgM+ B cells can phagocytose, like mammalian B1 cells, and secrete Ag-specific IgM, like mammalian B2 cells. Therefore, teleost IgM+ B cells may have the functions of both mammalian B1 and B2 cells. To support this view, we initially found that grass carp (Ctenopharyngodon idella) IgM+ plasma cells (PCs) exhibit robust phagocytic ability, akin to IgM+ naive B cells. Subsequently, we sorted grass carp IgM+ PCs into two subpopulations: nonphagocytic (Pha-IgM+ PCs) and phagocytic IgM+ PCs (Pha+IgM+ PCs), both of which demonstrated the capacity to secrete natural IgM with LPS and peptidoglycan binding capacity. Remarkably, following immunization of grass carp with an Ag, we observed that both Pha-IgM+ PCs and Pha+IgM+ PCs could secrete Ag-specific IgM. Furthermore, in vitro concatenated phagocytosis experiments in which Pha-IgM+ PCs from an initial phagocytosis experiment were sorted and exposed again to beads confirmed that these cells also have phagocytic capabilities, thereby suggesting that all teleost IgM+ B cells have phagocytic potential. Additionally, we found that grass carp IgM+ PCs display classical phenotypic features of macrophages, providing support for the hypothesis that vertebrate B cells evolved from ancient phagocytes. These findings together reveal that teleost B cells are a primitive B cell type with functions reminiscent of both mammalian B1 and B2 cells, providing insights into the origin and evolution of B cells in vertebrates.


Asunto(s)
Linfocitos B , Carpas , Inmunoglobulina M , Fagocitosis , Células Plasmáticas , Animales , Carpas/inmunología , Inmunoglobulina M/inmunología , Fagocitosis/inmunología , Células Plasmáticas/inmunología , Linfocitos B/inmunología , Fagocitos/inmunología , Evolución Biológica
2.
J Am Chem Soc ; 146(8): 5678-5692, 2024 Feb 28.
Artículo en Inglés | MEDLINE | ID: mdl-38359327

RESUMEN

The rapid and controlled synthesis of high-molecular-weight (HMW) polysarcosine (pSar), a potential polyethylene glycol (PEG) alternative, via the ring-opening polymerization (ROP) of N-carboxyanhydride (NCA) is rare and challenging. Here, we report the well-controlled ROP of sarcosine NCA (Sar-NCA) that is catalyzed by various carboxylic acids, which accelerate the polymerization rate up to 50 times, and enables the robust synthesis of pSar with an unprecedented ultrahigh molecular weight (UHMW) up to 586 kDa (DP ∼ 8200) and exceptionally narrow dispersity (D̵) below 1.05. Mechanistic experiments and density functional theory calculations together elucidate the role of carboxylic acid as a bifunctional catalyst that significantly facilitates proton transfer processes and avoids charge separation and suggest the ring opening of NCA, rather than decarboxylation, as the rate-determining step. UHMW pSar demonstrates improved thermal and mechanical properties over the low-molecular-weight counterparts. This work provides a simple yet highly efficient approach to UHMW pSar and generates a new fundamental understanding useful not only for the ROP of Sar-NCA but also for other NCAs.

3.
Cancer Control ; 31: 10732748241271682, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-39105433

RESUMEN

BACKGROUND: The effect of neoadjuvant chemotherapy (NACT) in gallbladder cancer (GBC) patients remains controversial. The aim of this study was to assess the impact of NACT on overall survival (OS) and cancer specific survival (CSS) in patients with localized or locoregionally advanced GBC, and to explore possible protective predictors for prognosis. METHODS: Data for patients with localized or locoregionally advanced GBC (i.e., categories cTx-cT4, cN0-2, and cM0) from 2004 to 2020 were collected from the Surveillance, Epidemiology, and End Results (SEER) database. Patients in the NACT and non-NACT groups were propensity score matched (PSM) 1:3, and the Kaplan-Meier method and log-rank test were performed to analyze the impact of NACT on OS and CSS. Univariable and multivariable Cox regression models were applied to identify the possible prognostic factors. Subgroup analysis was conducted to identify patients who would benefit from NACT. RESULTS: Of the 2676 cases included, 78 NACT and 234 non-NACT patients remained after PSM. In localized or locoregionally advanced GBC patients, the median OS of the NACT and non-NACT was 31 and 16 months (log-rank P < 0.01), and the median CSS of NACT and non-NACT was 32 and 17 months (log-rank P < 0.01), respectively. Longer median OS (31 vs 17 months, log-rank P < 0.01) and CSS (32 vs 20 months, log-rank P < 0.01) was associated with NACT compared with surgery alone. Multivariable Cox regression analysis showed that NACT, stage, and surgery type were prognostic factors for OS and CSS in GBC patients. Subgroup analysis revealed that the survival hazard ratios (HRs) of NACT vs non-NACT for localized or locoregionally advanced GBC patients were significant in most subgroups. CONCLUSIONS: NACT may provide therapeutic benefits for localized or locoregionally advanced GBC patients, especially for those with advanced stage, node-positive, poorly differentiated or undifferentiated disease. NACT combined with radical surgery was associated with a survival advantage. Therefore, NACT combined with surgery may provide a better treatment option for resectable GBC patients.


Asunto(s)
Neoplasias de la Vesícula Biliar , Terapia Neoadyuvante , Puntaje de Propensión , Programa de VERF , Humanos , Neoplasias de la Vesícula Biliar/patología , Neoplasias de la Vesícula Biliar/mortalidad , Neoplasias de la Vesícula Biliar/tratamiento farmacológico , Neoplasias de la Vesícula Biliar/terapia , Femenino , Masculino , Terapia Neoadyuvante/métodos , Terapia Neoadyuvante/estadística & datos numéricos , Persona de Mediana Edad , Pronóstico , Anciano , Quimioterapia Adyuvante/estadística & datos numéricos , Quimioterapia Adyuvante/métodos , Estadificación de Neoplasias , Estimación de Kaplan-Meier
4.
J Org Chem ; 89(21): 15979-15989, 2024 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-39436351

RESUMEN

A mild approach for synthesizing CF3-substituted ß-aza-spiroindolines and ß-carbolines from tryptamine-derived isocyanides via site-selective radical annulations has been reported. The crucial role of C2 substituents in the selective annulation process has been clarified. The approach shows good generality and practical applicability, highlighting its effectiveness and versatility.

5.
J Org Chem ; 89(5): 3657-3665, 2024 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-38366991

RESUMEN

A practical and regioselective direct N-alkylation of 2-pyridones is enabled by use of α-keto esters in the P(NMe2)3-mediated deoxygenation process. The reaction proceeds under mild conditions to produce N-alkylated 2-pyridones with high selectivity and generality, and the protocol is shown to be applicable for the scale-up synthesis, which makes it promising for practical applications.

6.
J Org Chem ; 89(16): 11777-11782, 2024 Aug 16.
Artículo en Inglés | MEDLINE | ID: mdl-39115151

RESUMEN

An efficient synthesis of cyanohydrin esters via a P(NMe2)3 mediated direct deoxygenation process has been exploited, circumventing the release or transformation of the CN─ anion during the reaction. This approach possesses a broad scope and acts as a powerful supplement for the construction of diverse cyanohydrin esters. It offers advantages such as mild conditions, straightforward operations, and excellent scalability, affirming the feasibility and versatility of this approach and highlighting its potential in practical synthesis.

7.
J Immunol ; 2022 Oct 24.
Artículo en Inglés | MEDLINE | ID: mdl-36426989

RESUMEN

Complement peptides C3a, C4a, and C5a are important components of innate immunity in vertebrates. Although they diverged from a common ancestor, only C3a and C4a can act as antibacterial peptides in Homo sapiens, suggesting that C5a has evolved into a purely chemotactic molecule; however, the antibacterial properties of C3a, C4a, and C5a across vertebrates still require elucidation. In this article, we show that, unlike those in H. sapiens, Mus musculus C3a, C4a, and C5a all possess antibacterial activities, implying that the antibacterial properties of C3a, C4a, and C5a have evolved divergently in vertebrates. The extremely different net charge, a key factor determining the antibacterial activities of cationic antimicrobial peptides, of vertebrate C3a, C4a, and C5a supports this speculation. Moreover, the antibacterial activity of overlapping peptides covering vertebrate C3a, C4a, and C5a further strongly supports the speculation, because their activity is positively correlated with the net charge of source molecules. Notably, the structures of C3a, C4a, and C5a are conserved in vertebrates, and the inactive overlapping peptides can become antibacterial peptides if mutated to possess enough net positive charges, indicating that net charge is the only factor determining the antibacterial properties of vertebrate C3a, C4a, and C5a. More importantly, many vertebrate C3a-, C4a-, and C5a-derived peptides possess high antibacterial activities yet exhibit no hemolytic activities, suggesting the application potential in anti-infective therapy. Taken together, our findings reveal that vertebrate C3a, C4a, and C5a are all sources of antibacterial peptides that will facilitate the design of excellent peptide antibiotics.

8.
J Immunol ; 208(8): 2037-2053, 2022 04 15.
Artículo en Inglés | MEDLINE | ID: mdl-35365566

RESUMEN

In vertebrates, leukocyte-derived chemotaxin-2 (LECT2) is an important immunoregulator with conserved chemotactic and phagocytosis-stimulating activities to leukocytes during bacterial infection. However, whether LECT2 possesses direct antibacterial activity remains unknown. In this article, we show that, unlike tetrapods with a single LECT2 gene, two LECT2 genes exist in teleost fish, named LECT2-a and LECT2-b Using grass carp as a research model, we found that the expression pattern of grass carp LECT2-a (gcLECT2-a) is more similar to that of LECT2 in tetrapods, while gcLECT2-b has evolved to be highly expressed in mucosal immune organs, including the intestine and skin. Interestingly, we found that gcLECT2-b, with conserved chemotactic and phagocytosis-stimulating activities, can also kill Gram-negative and Gram-positive bacteria directly in a membrane-dependent and a non-membrane-dependent manner, respectively. Moreover, gcLECT2-b could prevent the adherence of bacteria to epithelial cells through agglutination by targeting peptidoglycan and lipoteichoic acid. Further study revealed that gcLECT2-b can protect grass carp from Aeromonas hydrophila infection in vivo, because it significantly reduces intestinal necrosis and tissue bacterial load. More importantly, we found that LECT2 from representative tetrapods, except human, also possesses direct antibacterial activities, indicating that the direct antibacterial property of LECT2 is generally conserved in vertebrates. Taken together, to our knowledge, our study discovered a novel function of LECT2 in the antibacterial immunity of vertebrates, especially teleost fish, greatly enhancing our knowledge of this important molecule.


Asunto(s)
Carpas , Enfermedades de los Peces , Infecciones por Bacterias Gramnegativas , Aeromonas hydrophila , Animales , Antibacterianos , Carpas/metabolismo , Proteínas de Peces/genética , Proteínas de Peces/metabolismo , Inmunidad Innata , Leucocitos/metabolismo
9.
J Immunol ; 2022 Oct 24.
Artículo en Inglés | MEDLINE | ID: mdl-36280254

RESUMEN

Complement peptides C3a, C4a, and C5a are important components of innate immunity in vertebrates. Although they diverged from a common ancestor, only C3a and C4a can act as antibacterial peptides in Homo sapiens, suggesting that C5a has evolved into a purely chemotactic molecule; however, the antibacterial properties of C3a, C4a, and C5a across vertebrates still require elucidation. In this article, we show that, unlike those in H. sapiens, Mus musculus C3a, C4a, and C5a all possess antibacterial activities, implying that the antibacterial properties of C3a, C4a, and C5a have evolved divergently in vertebrates. The extremely different net charge, a key factor determining the antibacterial activities of cationic antimicrobial peptides, of vertebrate C3a, C4a, and C5a supports this speculation. Moreover, the antibacterial activity of overlapping peptides covering vertebrate C3a, C4a, and C5a further strongly supports the speculation, because their activity is positively correlated with the net charge of source molecules. Notably, the structures of C3a, C4a, and C5a are conserved in vertebrates, and the inactive overlapping peptides can become antibacterial peptides if mutated to possess enough net positive charges, indicating that net charge is the only factor determining the antibacterial properties of vertebrate C3a, C4a, and C5a. More importantly, many vertebrate C3a-, C4a-, and C5a-derived peptides possess high antibacterial activities yet exhibit no hemolytic activities, suggesting the application potential in anti-infective therapy. Taken together, our findings reveal that vertebrate C3a, C4a, and C5a are all sources of antibacterial peptides that will facilitate the design of excellent peptide antibiotics.

10.
Acta Pharmacol Sin ; 45(8): 1701-1714, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38609562

RESUMEN

Signal transducer and activator of transcription 3 (STAT3) plays an important role in the occurrence and progression of tumors, leading to resistance and poor prognosis. Activation of STAT3 signaling is frequently detected in hepatocellular carcinoma (HCC), but potent and less toxic STAT3 inhibitors have not been discovered. Here, based on antisense technology, we designed a series of stabilized modified antisense oligonucleotides targeting STAT3 mRNA (STAT3 ASOs). Treatment with STAT3 ASOs decreased the STAT3 mRNA and protein levels in HCC cells. STAT3 ASOs significantly inhibited the proliferation, survival, migration, and invasion of cancer cells by specifically perturbing STAT3 signaling. Treatment with STAT3 ASOs decreased the tumor burden in an HCC xenograft model. Moreover, aberrant STAT3 signaling activation is one of multiple signaling pathways involved in sorafenib resistance in HCC. STAT3 ASOs effectively sensitized resistant HCC cell lines to sorafenib in vitro and improved the inhibitory potency of sorafenib in a resistant HCC xenograft model. The developed STAT3 ASOs enrich the tools capable of targeting STAT3 and modulating STAT3 activity, serve as a promising strategy for treating HCC and other STAT3-addicted tumors, and alleviate the acquired resistance to sorafenib in HCC patients. A series of novel STAT3 antisense oligonucleotide were designed and showed potent anti-cancer efficacy in hepatocellular carcinoma in vitro and in vivo by targeting STAT3 signaling. Moreover, the selected STAT3 ASOs enhance sorafenib sensitivity in resistant cell model and xenograft model.


Asunto(s)
Antineoplásicos , Carcinoma Hepatocelular , Proliferación Celular , Resistencia a Antineoplásicos , Neoplasias Hepáticas , Factor de Transcripción STAT3 , Sorafenib , Factor de Transcripción STAT3/metabolismo , Factor de Transcripción STAT3/antagonistas & inhibidores , Carcinoma Hepatocelular/tratamiento farmacológico , Carcinoma Hepatocelular/patología , Carcinoma Hepatocelular/metabolismo , Sorafenib/farmacología , Sorafenib/uso terapéutico , Humanos , Neoplasias Hepáticas/tratamiento farmacológico , Neoplasias Hepáticas/patología , Neoplasias Hepáticas/metabolismo , Animales , Resistencia a Antineoplásicos/efectos de los fármacos , Antineoplásicos/farmacología , Antineoplásicos/uso terapéutico , Proliferación Celular/efectos de los fármacos , Línea Celular Tumoral , Ratones Desnudos , Oligonucleótidos Antisentido/farmacología , Oligonucleótidos Antisentido/uso terapéutico , Ratones , Ratones Endogámicos BALB C , Ensayos Antitumor por Modelo de Xenoinjerto , Movimiento Celular/efectos de los fármacos , Masculino , Transducción de Señal/efectos de los fármacos , Oligonucleótidos/farmacología
11.
Ann Vasc Surg ; 2024 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-39032593

RESUMEN

BACKGROUND: In recent years, compression therapy has attracted gradually increasing clinical attention in lower extremity venous diseases. However, basic concepts and clear nomenclature, standard treatment methods, and consistent product standards for pressure equipment are lacking. Therefore, developing clinical guidelines for compression therapy is essential to improving the treatment of venous diseases. METHODS: Our panel generated strong (grade I), moderate (grade IIa and IIb), and weak (grade III) recommendations based on high-quality (class A), moderate-quality (class B), and low-quality (class C) evidence, using the Grading of Recommendations, Assessment, Development, and Evaluations (GRADE) approach and the European Society of Cardiology (ESC) grading system. RESULTS: The panels made 30 recommendations from current evidence, focusing on 7 fields of lower extremity venous disease (venous thromboembolism, post-thrombotic syndrome (PTS), chronic venous insufficiency (CVI), varicose veins, hemangioma and vascular malformations, lymphedema, and venous ulcers) and 18 topics. CONCLUSIONS: Of the 30 recommendations made across the 18 topics, 7 were strong (grade I) and 17 were based on high-quality (class A) evidence, highlighting the need for further research of the use of compression therapy.

12.
BMC Public Health ; 24(1): 865, 2024 Mar 20.
Artículo en Inglés | MEDLINE | ID: mdl-38509529

RESUMEN

BACKGROUND: Following China's official designation as malaria-free country by WHO, the imported malaria has emerged as a significant determinant impacting the malaria reestablishment within China. The objective of this study is to explore the application prospects of machine learning algorithms in imported malaria risk assessment of China. METHODS: The data of imported malaria cases in China from 2011 to 2019 was provided by China CDC; historical epidemic data of malaria endemic country was obtained from World Malaria Report, and the other data used in this study are open access data. All the data processing and model construction based on R, and map visualization used ArcGIS software. RESULTS: A total of 27,088 malaria cases imported into China from 85 countries between 2011 and 2019. After data preprocessing and classification, clean dataset has 765 rows (85 * 9) and 11 cols. Six machine learning models was constructed based on the training set, and Random Forest model demonstrated the best performance in model evaluation. According to RF, the highest feature importance were the number of malaria deaths and Indigenous malaria cases. The RF model demonstrated high accuracy in forecasting risk for the year 2019, achieving commendable accuracy rate of 95.3%. This result aligns well with the observed outcomes, indicating the model's reliability in predicting risk levels. CONCLUSIONS: Machine learning algorithms have reliable application prospects in risk assessment of imported malaria in China. This study provides a new methodological reference for the risk assessment and control strategies adjusting of imported malaria in China.


Asunto(s)
Malaria , Humanos , Reproducibilidad de los Resultados , Malaria/epidemiología , Medición de Riesgo , China/epidemiología , Aprendizaje Automático
13.
Nano Lett ; 23(20): 9399-9405, 2023 Oct 25.
Artículo en Inglés | MEDLINE | ID: mdl-37877237

RESUMEN

An accurate rule for predicting conductance is the cornerstone of developing molecular circuits and provides a promising solution for miniaturizing electric circuits. The successful prediction of series molecular circuits has proven the possibility of establishing a rule for molecular circuits under quantum mechanics. However, the quantitatively accurate prediction has not been validated by experiments for parallel molecular circuits. Here we used 1,3-dihydrobenzothiophene (DBT) to build the parallel molecular circuits. The theoretical simulation and single-molecule conductance measurements demonstrated that the conductance of the molecule containing one DBT is the unprecedented linear combination of the conductance of the two individual channels with respective contribution weights of 0.37 and 0.63. With these weights, the conductance of the molecule containing two DBTs is predicted as 1.81 nS, matching perfectly with the measured conductance (1.82 nS). This feature offers a potential rule for quantitatively predicting the conductance of parallel molecular circuits.

14.
Angew Chem Int Ed Engl ; 63(45): e202411630, 2024 Nov 04.
Artículo en Inglés | MEDLINE | ID: mdl-39073287

RESUMEN

Polythioesters (PTEs) are emerging sustainable polymers for their degradability and recyclability. However, low polymerizability of monomers and extensive side reactions often hampered the polymerization process. Moreover, copolymers containing both thioester and other types of functional groups in the backbone are highly desirable but rarely accomplished owing to several synthetic challenges. Here, we report the ring-opening cascade polymerization (ROCAP) of N-(2-(acetylthio)ethyl)-glycine N-carboxyanhydrides (TE-NCA) to afford recyclable PTEs and unprecedented poly(thioester-co-peptoid)s (P(TE-co-PP)s) in a controlled manner. By developing appropriated carboxylic acid-tertiary amine dual catalysts, intramolecular S-to-N acyl shift is coupled into the ROCAP process of TE-NCA to yield products with dispersity below 1.10, molecular weight (Mn) up to 84.5 kDa, and precisely controlled ratio of thioester to peptoids. Random copolymerization of sarcosine NCA (Sar-NCA) and TE-NCA gives thioester-embedded polysarcosine with facile backbone degradation while maintaining the water solubility. This work represents a paradigm shift for the ROP of NCAs, enriches the realm of cascade polymerizations, and provides a powerful synthetic approach to functional PTEs and P(TE-co-PP)s that are otherwise difficult or impossible to make.

15.
Angew Chem Int Ed Engl ; : e202413653, 2024 Aug 12.
Artículo en Inglés | MEDLINE | ID: mdl-39133139

RESUMEN

In acidic proton exchange membrane water electrolysis (PEMWE), the anode oxygen evolution reaction (OER) catalysts rely heavily on the expensive and scarce iridium-based materials. Ruthenium dioxide (RuO2) with lower price and higher OER activity, has been explored for the similar task, but has been restricted by the poor stability. Herein, we developed an anion modification strategy to improve the OER performance of RuO2 in acidic media. The designed multicomponent catalyst based on sulfate anchored on RuO2/MoO3 displays a low overpotential of 190 mV at 10 mA cm-2 and stably operates for 500 hours with a very low degradation rate of 20 µV h-1 in acidic electrolyte. When assembled in a PEMWE cell, this catalyst as an anode shows an excellent stability at 500 mA cm-2 for 150 h. Experimental and theoretical results revealed that MoO3 could stabilize sulfate anion on RuO2 surface to suppress its leaching during OER. Such MoO3-anchored sulfate not only reduces the formation energy of *OOH intermediate on RuO2, but also impedes both the surface Ru and lattice oxygen loss, thereby achieving the high OER activity and exceptional durability.

16.
Angew Chem Int Ed Engl ; : e202414524, 2024 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-39384539

RESUMEN

Solid-state lithium metal batteries (SSLMBs) with solid polymer electrolyte (SPE) are highly promising for next-generation energy storage due to their enhanced safety and energy density. However, the stability of the solid electrolyte interphase (SEI) on the lithium metal/SPE interface is a major challenge, as continuous SEI degradation and regeneration during cycling lead to capacity fading. This article investigates the SEI formation on lithium anodes (l-SEI) and composite lithium anodes (c-SEI) in solid-state lithium metal batteries. The composite anodes form a uniform Li2S-rich inorganic SEI layer and a thinner organic SEI layer, effectively passivating the interface for enhanced cycling stability. Specifically, the full cells with c-SEI anodes sustain over 400 cycles at 0.5 C under a high areal capacity of 2.0 mAh cm-2. Moreover, the reversible high-loading solid-state pouch cells exhibit exceptional safety even after curling and cutting. These findings offer valuable insights into developing composite electrodes with robust SEI for solid-state polymer-based lithium metal batteries.

17.
J Am Chem Soc ; 145(31): 17087-17095, 2023 Aug 09.
Artículo en Inglés | MEDLINE | ID: mdl-37523458

RESUMEN

Transition-metal-catalyzed [4 + 1] reaction of dienes and carbon monoxide (CO) is the most straightforward and easily envisioned cyclization for the synthesis of five-membered carbocycles, which are ubiquitously found in natural products and functional molecules. Unfortunately, no test of this reaction was reported, and consequently, chemists do not know whether such kind of reaction works or not. Herein, we report that the [4 + 1] reaction of common dienes and CO cannot work, at least under the catalysis of [Rh(cod)Cl]2. However, using cyclopropyl-capped dienes (also named allylidenecyclopropanes) as substrates, the corresponding [4 + 1] reaction with CO proceeds smoothly in the presence of [Rh(cod)Cl]2. This [4 + 1] reaction, with a broad scope, provides efficient access to five-membered carbocyclic compounds of spiro[2.4]hept-6-en-4-ones. The [4 + 1] cycloadducts can be further transformed into other molecules by using the unique chemistry of cyclopropyl groups present in these molecules. The mechanism of this [4 + 1] reaction has been investigated by quantum chemical calculations, uncovering that cyclopropyl-capped dienes are strained dienes and the oxidative cyclization step in the [4 + 1] catalytic cycle can release this (angular) strain both kinetically and thermodynamically. The strain release in this step then propagates to all followed CO coordination/CO insertion/reductive elimination steps in the [4 + 1] catalytic cycle, helping the realization of this cycloaddition reaction. In contrast, common dienes (including cyclobutyl-capped dienes) do not have such advantages and their [4 + 1] reaction suffers from energy penalty in all steps involved in the [4 + 1] catalytic cycle. The reactivity of ene-allenes for the [4 + 1] reaction with CO is also discussed.

18.
Small ; 19(19): e2208274, 2023 May.
Artículo en Inglés | MEDLINE | ID: mdl-36776020

RESUMEN

With rapid and continuous consumption of nonrenewable energy, solar energy can be utilized to meet the energy requirement and mitigate environmental issues in the future. To attain a sustainable society with an energy mix predominately dependent on solar energy, photoelectrochemical (PEC) device, in which semiconductor nanostructure-based photocatalysts play important roles, is considered to be one of the most promising candidates to realize the sufficient utilization of solar energy in a low-cost, green, and environmentally friendly manner. Interface engineering of semiconductor nanostructures has been qualified in the efficient improvement of PEC performances including three basic steps, i.e., light absorption, charge transfer/separation, and surface catalytic reaction. In this review, recently developed interface engineering of semiconductor nanostructures for direct and high-efficiency conversion of sunlight into available forms (e.g., chemical fuels and electric power) are summarized in terms of their atomic constitution and morphology, electronic structure and promising potential for PEC applications. Extensive efforts toward the development of high-performance PEC applications (e.g., PEC water splitting, PEC photodetection, PEC catalysis, PEC degradation and PEC biosensors) are also presented and appraised. Last but not least, a brief summary and personal insights on the challenges and future directions in the community of next-generation PEC devices are also provided.

19.
Chemistry ; 29(37): e202300641, 2023 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-37052175

RESUMEN

Lewis base catalyzed allylations of C-centered nucleophiles have been largely limited to the niche substrates with acidic C-H substituted for C-F bonds at the stabilized carbanionic carbon. Herein we report that the concept of latent pronucleophiles serves to overcome these limitations and allow for a variety of common stabilized C-nucleophiles, when they are introduced as the corresponding silylated compounds, to undergo enantioselective allylations using allylic fluorides. The reactions of silyl enol ethers afford the allylation products in good yields and with high degree of regio/stereoselectivity as well as diastereoselectivity when cyclic silyl enol ethers are used. Further examples of silylated stabilized carbon nucleophiles that undergo efficient allylation speak in favor of the general applicability of this concept to C-centered nucleophiles.

20.
Inorg Chem ; 62(22): 8647-8654, 2023 Jun 05.
Artículo en Inglés | MEDLINE | ID: mdl-37219913

RESUMEN

The development of the most promising electro-catalysts for the high-performance hydrogen evolution reaction (HER) in neutral media is exceedingly desirable. Here, the convenient hydrothermal reaction of PbI2, 3-pyrazinyl-1,2,4-triazole (3-pt), KI, and methanol in HI aqueous solution acquired an organic hybrid iodoplumbate [mtp][Pb2I5][PbI3]·0.5H2O (denoted as PbI-1, mtp2+ = 3-(1,4-dimethyl-1H-1,2,4-triazol-4-ium-3-yl)-1-methylpyrazin-1-ium), which not only provided an infrequent in situ organic mtp2+ cation that originated from the hydrothermal N-methylation reaction of 3-pt in acidic KI solution but also offered the rare example of organic hybrid iodoplumbate incorporating both one-dimensional (1-D) [PbI3-]n and two-dimensional (2-D) [Pb2I5-]n polymeric anions with one configuration of the mtp2+ cation. PbI-1 was applied for the construction of a Ni nanoparticle decorating the PbI-1 electrode (Ni/PbI-1/NF) via successive coating and electrodeposition onto the porous Ni foam (NF) support. The fabricated Ni/PbI-1/NF electrode that served as the cathodic catalyst showed excellent HER electro-catalytic activity.

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