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1.
Org Lett ; 2022 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-35532347

RESUMO

Direct electrocarboxylation of various N-acylimines with atmospheric CO2 is achieved in an undivided cell under mild conditions, affording substituted α-amino acids in yields of 62-95%. This reaction is conducted with high efficiency using triethanolamine as an external reductant under nonsacrificial anode conditions, and can be facilely performed on gram scale. Preliminary mechanistic studies including cyclic voltammetry and control experiments support N-radical carbanion as the key intermediate.

2.
Artigo em Inglês | MEDLINE | ID: mdl-35575978

RESUMO

Transition-metal-catalyzed copolymerization of ethylene with carbon monoxide affords polyketones materials with excellent mechanical strength, photodegradability, surface and barrier properties. Unlike the widely used and rather expensive Pd catalysts, Ni-catalyzed carbonylative polymerization is very difficult since the strong binding affinity of CO to Ni deactivates the highly electrophilic metal center easily. In this study, various cationic [P,O]-coordinated Ni complexes were synthesized using the electronic modulation strategy, and the catalyst with strong electron-donating substituents exhibits an excellent productivity of 10 4 g polymer (g Ni) -1 , which represents a rare discovery that Ni complex could operate with such exceptional efficiency in comparison with Pd catalysts. Notably, those Ni catalysts were also efficient for terpolymerization of ethylene, propylene with CO for producing commercial polyketone materials with low melting temperatures and easy processibility.

3.
Angew Chem Int Ed Engl ; 61(22): e202202585, 2022 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-35229423

RESUMO

Asymmetric copolymerization of meso-epoxide and anhydride is a powerful strategy for preparing various isotactic polyesters with two contiguous stereogenic centers. However, the previous binary systems suffered from slow rates at low loadings, poor enantioselectivities and transesterification reactions at enhanced temperatures. Herein, we report novel dinuclear aluminium complexes with multiple chiralities and ammonium salts anchored on ligand frameworks. These bifunctional catalysts exhibit high activities and enantioselectivities for epoxides/anhydrides copolymerizations at harsh conditions via intramolecularly synergistic catalysis, affording polyesters with unprecedented molecular weights and narrow distributions. Notably, no transesterification reactions were observed, significantly different from the binary catalyst/cocatalyst pairs. This study represents a rare example regarding temperature-independent asymmetric induction for preparing chiral polymers from achiral monomers.

4.
Angew Chem Int Ed Engl ; 61(16): e202115950, 2022 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-35129257

RESUMO

The usage of elemental sulfur (S8 ) for constructing sulfur-containing polymers is of great significance in terms of sulfur resource utilization or fabrication of high-performance polymers. Currently, the random disassembly of S8 hinders its direct use in the precise synthesis of sulfur-containing polymers. Herein, we provide an effective strategy for controlling the dismantlement of S8 to synthesize polydisulfides, a promising category of dynamic bonds containing polymers. In this strategy, the completely alternating copolymerization of one sulfur atom, which is orderly derived from S8 , with episulfides is achieved with MTBD (7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene) as catalyst and [PPN]SbF6 ([PPN]+ is bis(triphenylphosphine)iminium) as cocatalyst. Delightedly, the living- polymerization feature, and the good monomer compatibility allows for the access to diverse polydisulfides. Furthermore, the density functional theory (DFT) was employed to elaborate the copolymerization process.

5.
Zool Res ; 43(1): 98-110, 2022 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-34904422

RESUMO

As a highly important fish virus, nervous necrosis virus (NNV) has caused severe economic losses to the aquaculture industry worldwide. Autophagy, an evolutionarily conserved intracellular degradation process, is involved in the pathogenesis of several viruses. Although NNV can induce autophagy to facilitate infection in grouper fish spleen cells, how it initiates and mediates autophagy pathways during the initial stage of infection is still unclear. Here, we found that red-spotted grouper NNV (RGNNV) induced autophagosome formation in two fish cell lines at 1.5 and 3 h post infection, indicating that autophagy is activated upon entry of RGNNV. Moreover, autophagic detection showed that RGNNV entry induced incomplete autophagy by impairing the fusion of autophagosomes with lysosomes. Further investigation revealed that binding of the RGNNV capsid protein (CP) to the Lateolabrax japonicus heat shock protein HSP90ab1 (LjHSP90ab1), a cell surface receptor of RGNNV, contributed to RGNNV invasion-induced autophagy. Finally, we found that CP blocked the interaction of L. japonicus protein kinase B (AKT) with LjHSP90ab1 by competitively binding the NM domain of LjHSP90ab1 to inhibit the AKT-mechanistic target of the rapamycin (MTOR) pathway. This study provides novel insight into the relationship between NNV receptors and autophagy, which may help clarify the pathogenesis of NNV.


Assuntos
Bass , Proteínas do Capsídeo , Doenças dos Peixes , Nodaviridae , Infecções por Vírus de RNA , Animais , Autofagia , Proteínas do Capsídeo/fisiologia , Doenças dos Peixes/virologia , Proteínas de Peixes , Necrose/veterinária , Proteínas Proto-Oncogênicas c-akt , Infecções por Vírus de RNA/veterinária , Serina-Treonina Quinases TOR , Virulência
6.
Org Biomol Chem ; 20(3): 678-685, 2022 01 19.
Artigo em Inglês | MEDLINE | ID: mdl-34939627

RESUMO

Herein, we present the first organocatalytic oxygen/sulfur atom exchange reaction (O/S ER) of isatins by employing carbonyl sulfide (COS) as a novel sulfuring reagent under mild reaction conditions. 8-Diazabicyclo[5.4.0]undec-7-ene (DBU) exhibited excellent activity in this approach. Remarkably, the chemical transformations of in situ generated 3-thioisatins can be tuned via the judicious choice of reaction solvents in a one pot process, enabling the selective formation of either functionalized isoindigos in CH3CN via a self-condensation process or spirothiopyrans in DMSO in the presence of conjugated dienes via the thio-Diels-Alder reaction. Mechanistic studies with experimental and density functional theory approaches revealed that the O/S ER between isatins and COS results in the formation of 3-thioisatins as the key intermediates, which further undergo solvent-controlled transformations to generate isoindigos or spirothiopyrans, respectively. The easily-accessible substrates and operational simplicity make the process suitable for further exploration. The practicality of this transformation was demonstrated by the gram-scale synthesis of isoindigo-based drug molecules and donor-acceptor conjugated polymers.

7.
Angew Chem Int Ed Engl ; 61(9): e202116208, 2022 02 21.
Artigo em Inglês | MEDLINE | ID: mdl-34964224

RESUMO

Polyhydroxyalkanoates (PHAs) are a unique class of commercially manufactured biodegradable polyesters with properties suitable for partially substituting petroleum-based plastics. However, high costs and low volumes of production have restricted their application as commodity materials. In this study, tri-metallic complexes were developed for carbonylative polymerization via a dual catalysis strategy, and 17 products of novel PHAs with up to 38.2 kg mol-1 Mn values were discovered. The polymerization proceeds in a sequential fashion, which entails the carbonylative ring expansion of epoxide to ß-lactone and its subsequent ring-opening polymerization that occurs selectively at the O-alkyl bond via carboxylate species. The wide availability and structural diversity of epoxide monomers provide PHAs with various structures, excellent functionalities, and tunable properties. This study represents a rare example of the preparation of PHAs using epoxides and carbon monoxide as raw materials.


Assuntos
Complexos de Coordenação/química , Compostos de Epóxi/química , Poli-Hidroxialcanoatos/síntese química , Catálise , Estrutura Molecular , Poli-Hidroxialcanoatos/química , Polimerização
8.
J Am Chem Soc ; 143(28): 10743-10750, 2021 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-34237217

RESUMO

Copolymerization of olefin with carbon monoxide has received considerable interest from both academia and industry, and the introduction of polar carbonyl group renders the resultant polyketones with excellent mechanical strength, crystallinity, photodegradability, hydrophilicity, surface, and barrier properties. However, most of the reported polyketones are difficult to be processed because of limited solubility in common solvents and high melting temperature (Tm ∼ 260 °C) resulting from the strictly alternative structure. Nonalternating copolymerization of ethylene with CO is a very promising method to circumvent the problem of processability of traditional perfectly alternating polyketone. In the contribution, the palladium coordinated diphosphazane monoxide substituted by strong electron-donating groups is discovered to be highly reactive for producing nonalternating polyketones, and up to 24.2% extra ethylene incorporation has lowered Tm values to 147 and 165 °C and further improved thermal stability (Td ∼ 339 °C) of the resultant materials. Our data demonstrates that cationic palladium complexes can also exhibit excellent reactivity and an unprecedented nonalternating degree in this copolymerization.

9.
Angew Chem Int Ed Engl ; 60(33): 17898-17903, 2021 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-34129266

RESUMO

We report the synthesis of isotactic azobenzene-based polyesters (azopolyesters) with main-chain chirality via highly enantioselective resolution copolymerization of racemic azobenzene-containing epoxides with cyclic anhydrides. All polyesters with trans-azobenzene moieties were found to be semicrystalline materials with melting temperatures of 153-231 °C, while the corresponding isotactic cis-azopolyesters were amorphous. The azobenzene groups in the copolymers exhibited reversible trans-to-cis and cis-to-trans photoisomerization upon irradiation with light. This demonstrates that the crystallinity of isotactic azopolyesters can be manipulated via photoinduced reversible isomerization. In addition, mixing isotactic trans-polyesters with different enantiomeric configurations in a 1:1 mass ratio afforded crystalline stereocomplexes for which the crystalline behavior differed significantly from those of the component enantiomer. Also, photoinduced reversible transitions between semicrystalline and amorphous states were observed in various stereocomplexes of isotactic trans-azopolyesters, similar to the isotactic azopolyesters themselves.

10.
Angew Chem Int Ed Engl ; 60(8): 4315-4321, 2021 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-33180984

RESUMO

Polymeric materials possessing both high refractive indices and high Abbe numbers are much in demand for the development of advanced optical devices. However, the synthesis of such functional materials is a challenge because of the trade-off between these two properties. Herein, a synthetic strategy is presented for enhancing the optical properties of CO2 -based polycarbonates by modifying the polymer's topological structure. Terpolymers with thiocarbonate and carbonate units randomly distributed in the polymers' main chain were synthesized via the terpolymerization of cyclohexene oxide with a mixture of CO2 and COS in the presence of metal catalysts, most notably a dinuclear aluminum complex. DFT calculations were employed to explain why different structural sequence were obtained with distinct bimetallic catalysts. Varying the CO2 pressure made it possible to obtain terpolymers with tunable carbonate linkages in the polymer chain. More importantly, optical property studies revealed that terpolymers with comparable thiocarbonate and carbonate units exhibited a refractive index of 1.501 with an enhanced Abbe number as high as 48.6, much higher than the corresponding polycarbonates or polythiocarbonates. Additionally, all terpolymers containing varying thiocarbonate content displayed good thermal properties with Tg >109 °C and Td >260 °C, suggesting little loss in the thermal stability compared to the polycarbonate. Hence, modification of the topological structure of the polycarbonate is an efficient method of obtaining polymeric materials with enhanced optical properties without compromising thermal performance.

11.
Angew Chem Int Ed Engl ; 60(11): 5994-6002, 2021 03 08.
Artigo em Inglês | MEDLINE | ID: mdl-33270965

RESUMO

Unprecedented enantioselective resolution copolymerization of racemic cis-internal epoxides and anhydrides was mediated by dinuclear aluminum complexes with multiple chirality, affording optically active polyesters with two contiguous stereogenic centers, and the unreacted substrates in good enantioselectivity. Unexpected stereoconvergence is observed in this resolution copolymerization, where the selectivity factor for the enantioselective formation of copolymer significantly exceeds the kinetic resolution coefficient based on the unreacted epoxide at various conversions. Catalytic activity and copolymer enantioselectivity are strongly influenced by the phenolate ortho-substituents of the ligand set, as well as the axial linker and its chirality. An enantiopure binaphthol-linked bimetallic AlIII complex allows stereoconvergent access to the stereoregular semi-crystalline polyesters and a concomitant kinetic resolution of the epoxide substrates.

12.
J Org Chem ; 85(17): 11579-11588, 2020 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-32786631

RESUMO

Cyclic anhydrides are versatile synthons and functional comonomers. Herein, we reported an organic base-promoted carboxylative cyclization of 2-butenoates with carbon dioxide to produce important glutaconic anhydrides in good yields. This metal-free reaction showed broad substrate scopes and proceeded under mild reaction conditions.

13.
J Clin Psychopharmacol ; 40(4): 386-390, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32618683

RESUMO

BACKGROUND: This was a meta-analysis of double-blind, randomized controlled trials that examined the therapeutic effects and tolerability of adjunctive fluvoxamine versus placebo for schizophrenia. METHODS: The Review Manager, Version 5.3, was used to analyze data. RESULTS: Five double-blind randomized controlled trials (N = 284) covering 145 patients on adjunctive fluvoxamine and 139 patients on placebo were included in the analyses. Meta-analyses of total psychopathology, and negative, positive, and depressive symptoms did not show significant differences between the fluvoxamine and placebo groups. Two studies examined the effects of adjunctive fluvoxamine on cognitive functioning with mixed findings. Fluvoxamine was superior over placebo in lessening weight gain and metabolic abnormalities. Although fluvoxamine led to more discontinuation, no significant group differences were found regarding adverse drug reactions. CONCLUSIONS: There was inconsistent evidence for the therapeutic effect of adjunctive fluvoxamine on cognitive functions and preliminary evidence for alleviating metabolic syndrome caused by clozapine. More studies are needed to explore further the effectiveness of adjunctive fluvoxamine for schizophrenia.


Assuntos
Fluvoxamina/uso terapêutico , Ensaios Clínicos Controlados Aleatórios como Assunto/estatística & dados numéricos , Esquizofrenia/tratamento farmacológico , Adolescente , Adulto , Idoso , Antipsicóticos/efeitos adversos , Antipsicóticos/uso terapêutico , Cognição/efeitos dos fármacos , Método Duplo-Cego , Quimioterapia Combinada/efeitos adversos , Feminino , Fluvoxamina/efeitos adversos , Humanos , Masculino , Pessoa de Meia-Idade , Resultado do Tratamento , Adulto Jovem
14.
Proc Natl Acad Sci U S A ; 117(27): 15429-15436, 2020 07 07.
Artigo em Inglês | MEDLINE | ID: mdl-32581124

RESUMO

The preparation of stereochemistry- and sequence-defined polymers, in which different monomer units are arranged in an ordered fashion just like biopolymers, is of great interest and has been a long-standing goal for chemists due to the expectation of unique macroscopic properties. Here, we describe the enantioselective terpolymerization of racemic terminal epoxides, meso-epoxides, and anhydrides mediated by the privileged chiral dinuclear Al(III) catalyst system, to afford optically active polyester terpolymers with either gradient or random distribution as determined by the epoxides employed during their preparation. The enantioselective terpolymerization of racemic tert-butyl glycidyl ether (rac-TBGE) and cyclopentene oxide with phthalic anhydride (PA) or naphthyl anhydride (NA) gives novel gradient polyesters, in which the crystallization behavior varies continuously along the main chain, due to the decrement of one ester component and the increment of the other occurring sequentially from one chain end to the other. In contrast, the enantioselective terpolymerization of rac-TBGE and meso-epoxide (cyclohexene oxide, 3,4-epoxytetrahydrofuran, or 1,4-dihydronaphthalene oxide) with an anhydride (PA or NA) provided chiral statistical terpolyesters with the random distribution of two kinds of ester units, resulting in a material possessing a mixed glass transition temperature. The present study therefore provides a convenient route to chiral polyesters bearing a range of physical and degradability properties.

15.
Angew Chem Int Ed Engl ; 59(32): 13633-13637, 2020 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-32372553

RESUMO

Topological polymers possess many advantages over linear polymers. However, when it comes to the poly(monothiocarbonate)s, no topological polymers have been reported. Described herein is a facile and efficient approach for synthesizing well-defined branched poly(monothiocarbonate)s in a "grafting through" manner by copolymerizing carbonyl sulfide (COS) with epichlorohydrin (ECH), where the side-chain forms in situ. The lengths of the side-chains are tunable based on reaction temperatures. More importantly, enhancement in thermal properties of the branched copolymer was observed, as the Tg  value increased by 22 °C, compared to the linear analogues. When chiral ECH was utilized, semicrystalline branched poly(monothiocarbonate)s were accessible with a Tm  value of 112 °C, which is 40 °C higher than that of the corresponding linear poly(monothiocarbonate)s. The strategy presented herein for synthesizing branched polymers provides efficient and concise access to topological polymers.

16.
Nat Chem ; 12(4): 324-326, 2020 04.
Artigo em Inglês | MEDLINE | ID: mdl-32221500
17.
Vet Immunol Immunopathol ; 221: 110009, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31945652

RESUMO

A 14-day experiment was conducted to explore the pathological process and immune response of soybean meal (SBM) induced enteritis (SBMIE) in grass carp (Ctenopharyngodon idellus). The complete replacement of dietary fish meal (FM) with SBM resulted in a remarkable reduction in final body weight, weight gain ratio, and feed conversion efficiency (p < 0.05). The typical histopathological changes of SBMIE appeared starting at day 4, and progressively increased in severity until day 8, then gradually subsided after day 11. The course of SBMIE could be divided into incubation period (days 1-2), prodromal period (days 3-6), symptomatic period (days 7-10), and convalescent period (days 11-14). Transcription levels of pro-inflammatory cytokines, including IL-1ß, TNF-α, IL-6, IL-8, IL-17A/F1 and IFN-γ2, were up-regulated during the prodromal period, and then down-regulated during the convalescent period. Transcript levels of anti-inflammatory cytokines (IL-10 and TGFß1) and their receptors (IL-10R1 and TßRII), were up-regulated during the prodromal and convalescent periods. Transcript levels of MHCIIß, Igµ, Igτ, TCRδ, TCRß, CD4, and CD8α were altered in SBMIE. Furthermore, expression levels of T-bet, IFN-γ2, RORγ2 and IL-17A/F1 were significantly increased in the initiation of enteritis, whereas the transcript levels of Foxp3 and IL-2/15Ra were significantly up-regulated in the repair of enteritis. In conclusion, grass carp SBMIE is regulated by the adjustment of SBM-based diet intake, and the changes of the above-mentioned genes expression suggest that these genes may be involved in SBMIE.


Assuntos
Ração Animal/análise , Carpas/imunologia , Citocinas/imunologia , Enterite/veterinária , Doenças dos Peixes/imunologia , Trato Gastrointestinal/imunologia , Soja/efeitos adversos , Animais , Carpas/metabolismo , Citocinas/genética , Suplementos Nutricionais , Enterite/induzido quimicamente , Enterite/imunologia , Doenças dos Peixes/induzido quimicamente , Trato Gastrointestinal/patologia , Inflamação/genética , Soja/química
18.
Org Biomol Chem ; 18(5): 905-911, 2020 02 07.
Artigo em Inglês | MEDLINE | ID: mdl-31915786

RESUMO

Organocatalyzed [4 + 2] annulation of CO2/COS with allenamides is firstly reported to synthesize 1,3-oxazine-2,4-diones and 1,3-thiazine-2,4-diones in moderate to excellent yields under mild reaction conditions. The catalytic potential of a series of Lewis base CO2 and COS adducts are particularly noted for this process, which features high regio- and chemo-selectivity, step-economy, facile scalability, and easy product derivatization. This study offers the potential for the application of organocatalytic systems for CO2 and COS chemical transformation.

19.
Fish Shellfish Immunol ; 97: 523-530, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31881328

RESUMO

Interferon (IFN) is a vital antiviral factor in host in the early stages after the viral invasion. Meanwhile, viruses have to survive by taking advantage of the cellular machinery and complete their replication. As a result, viruses evolved several immune escape mechanisms to inhibit host IFN expression. However, the mechanisms used to escape the host's IFN system are still unclear for infectious hematopoietic necrosis virus (IHNV). In this study, we report that the N protein of IHNV inhibits IFN1 production in rainbow trout by degrading the MITA. Firstly, the upregulation of IFN1 promoter activity stimulated by poly I:C was suppressed by IHNV infection. Consistent with this result, the overexpression of the N protein of IHNV blocked the IFN1 transcription that was activated by poly I:C and MITA. Secondly, MITA was remarkably decreased by the overexpression of N protein at the protein level. Further analysis demonstrated that the N protein targeted MITA and promoted the ubiquitination of MITA. Taken together, these data suggested that the production of rainbow trout IFN1 could be suppressed by the N protein of IHNV via degrading MITA.


Assuntos
Proteínas de Peixes/genética , Vírus da Necrose Hematopoética Infecciosa/imunologia , Interferons/imunologia , Proteínas de Membrana/genética , Proteínas do Nucleocapsídeo/imunologia , Oncorhynchus mykiss/imunologia , Animais , Antivirais/farmacologia , Células HEK293 , Interações entre Hospedeiro e Microrganismos/imunologia , Humanos , Vírus da Necrose Hematopoética Infecciosa/genética , Proteínas do Nucleocapsídeo/genética , Oncorhynchus mykiss/virologia , Poli I-C/farmacologia , Infecções por Rhabdoviridae , Ubiquitinação
20.
ChemSusChem ; 12(23): 5164-5171, 2019 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-31651092

RESUMO

The exponentially increasing viscosity of water-lean CO2 absorbents during carbon capture processes is a critical problem for practical application, owing to its strong correlation with systems' mass transfer properties, as well as convenience of transportation. In this work, a concise strategy based on structure-viscosity relationships is proposed and applied to construct a series of functionalized ethylenediamines as single-component absorbents for post-combustion CO2 capture. These nonaqueous absorbents have outstanding viscosities (50-200 cP, 25 °C) at their maximal CO2 capacities (up to 22 wt % or 4.92 mol kg-1 , 1 bar), and are readily regenerated at low temperatures (50-80 °C) under ambient pressure. Additional capture of CO2 through physisorption could also be achieved by operating at high pressures. The CO2 capture and release process is systematically investigated by means of 13 C NMR spectroscopy, differential scanning calorimetry (DSC), in situ FTIR analysis, and density functional theory (DFT) calculations, which could provide sufficient spectroscopic details to reveal the ease of reversibility and enable rational interpretation of the absorption mechanism.

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