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1.
J Hazard Mater ; 421: 126628, 2022 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-34343879

RESUMO

Electroreduction of nitrate (NO3-) to value-added ammonia (NH3) provides an alternative to NH3 production industry and remediation of NO3--containing wastewater. This study reports a series of Cu-Ni catalysts with component-controllable CuxNiy nanoparticles encapsulated in N-doped carbon film (CuxNiy/NC), and disclosure of the associated mechanism for NO3- reduction reaction (NO3-RR). Cu0.43Ni0.57/NC achieves a better NO3--N removal proportion of 89% in comparison with the reference catalysts, including Cu/NC (73%) and CuxNiy/NC with other compositions (Cu0.79Ni0.21/NC, 83%; Cu0.26Ni0.74/NC, 62%; Ni/NC, 20%). The experimental results and density functional theory calculations demonstrate that the lowered energy barriers of *NO2-to-*NO derived from appropriate Ni atom alloying plays a key role in the enhanced catalytic activity. Auxiliary porous substrate further contributes to the exposure of active sites and the durability of catalyst structure. These findings offer a mechanistic understanding of catalyst structure on the NO3-RR activity and valuable insights toward rational design of other catalysts for enhanced NO3-RR.

2.
Water Res ; 207: 117832, 2021 Nov 03.
Artigo em Inglês | MEDLINE | ID: mdl-34781183

RESUMO

Wastewater with high salinity is one of the major challenges for conventional wastewater treatment. Although nitrogen management is vital for wastewater treatment, efficient strategies for nitrogen recovery and removal from saline wastewater remain challenging. Here we propose microbial ammonium assimilation to achieve efficient nitrogen removal and recovery into biomass from saline wastewater without gaseous nitrogen release opposite to the conventional wastewater treatment, . We find one marine bacterium Psychrobacter aquimaris A4N01 with the ability to form sedimentary granular biofilms that can be engineered to construct an efficient ammonium-assimilating microbiome followed the bottom-up design. We demonstrate that the microbiome removes ammonium through assimilation without reactive nitrogen intermediates and gaseous nitrogen emission, according to the functional gene abundance and nitrogen balance. More than 80% of ammonium, total nitrogen and total phosphorus are removed and recovered into biomass, with more than 98% of COD removed from saline wastewater. As one prototypic microbe to form ammonium-assimilating biofilms, Psychrobacter aquimaris A4N01 plays key role in nutrient metabolism and microbiome construction. We stress that ammonium assimilation with a clear and short pathway is a promising method in future saline wastewater treatment and sustainable nitrogen management.

3.
Chem Sci ; 12(39): 13144-13150, 2021 Oct 13.
Artigo em Inglês | MEDLINE | ID: mdl-34745545

RESUMO

This report describes palladium-catalyzed C-H glycosylation and retro Diels-Alder tandem reaction via structurally modified norbornadienes (smNBDs). smNBDs were proposed to regulate the reactivity of the aryl-norbornadiene-palladacycle (ANP), including its high chemoselectivity and regioselectivity, which were the key to constructing C2 and C3 unsubstituted C4-glycosidic indoles. The scope of this substrate is extensive; the halogenated six-membered and five-membered glycosides were applied to the reaction smoothly, and N-alkyl (primary, secondary and tertiary) C4-glycosidic indoles can also be obtained by this method. In terms of mechanism, the key ANP intermediates characterized by X-ray single-crystal diffraction and further controlled experiments proved that the migration-insertion of smNBDs with phenylpalladium intermediate endows them with high chemo- and regioselectivity. Finally, density functional theory (DFT) calculation further verified the rationality of the mechanism.

4.
Org Lett ; 23(20): 7961-7965, 2021 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-34612651

RESUMO

This report describes a palladium-catalyzed Catellani reaction consisting of amination/[2 + 3] or [2 + 4] cyclization via a carboxylate ligand-exchange strategy. This method effectively activates ortho-substituents that avoid a second C-H palladation. The scope of substrates was broad, o-methyl-substituted iodoarenes were applied to the reaction smoothly, and o-phenyl-substituted iodoarenes can also be obtained by this method. In terms of mechanism, density functional theory calculations proved the sequence of the key five-membered aryl-norbornene-palladacycle intermediate formation and C(sp3 or sp2)-H activation.

5.
Int J Biol Sci ; 17(14): 3993-4004, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34671214

RESUMO

Prostaglandin D2 (PGD2) is the most abundant prostaglandin in the brain, but its involvement in brain damage caused by type 2 diabetes (T2D) has not been reported. In the present study, we found that increased PGD2 content is related to the inhibition of autophagy, which aggravates brain damage in T2D, and may be involved in the imbalanced expression of the corresponding PGD2 receptors DP1 and DP2. We demonstrated that DP2 inhibited autophagy and promotedT2D-induced brain damage by activating the PI3K/AKT/mTOR pathway, whereas DP1enhanced autophagy and amelioratedT2D brain damage by activating the cAMP/PKA pathway. In a T2D rat model, DP1 expression was decreased, and DP2 expression was increased; therefore, the imbalance in PGD2-DPs may be involved in T2D brain damage through the regulation of autophagy. However, there have been no reports on whether PKA can directly inhibit mTOR. The PKA catalytic subunit (PKA-C) has three subtypes (α, ß and γ), and γ is not expressed in the brain. Subsequently, we suggested that PKA could directly interact with mTOR through PKA-C(α) and PKA-C(ß). Our results suggest that the imbalance in PGD2-DPs is related to changes in autophagy levels in T2D brain damage, and PGD2 is involved in T2D brain damage by promoting autophagy via DP1-PKA/mTOR and inhibiting autophagy via DP2-PI3K/AKT/mTOR.

6.
Org Lett ; 23(19): 7518-7523, 2021 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-34505792

RESUMO

In palladium/norbornene (Pd/NBE) chemistry, the "ortho effect" has been proven to be a key factor in the process of ß-carbon elimination to extrude NBE. Herein, we found that the o-iodoaniline protected by a p-methoxybenzenesulfonyl group can recover the "ortho effect" and then undergo N-S bond cleavage with vinyl palladium, thus achieving a highly selective C-N coupling reaction in the Catallani-Lautens reaction system. On the basis of this discovery, a one-step synthesis of highly functionalized tricyclic indole derivatives was realized.

7.
Front Plant Sci ; 12: 707496, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34456948

RESUMO

Several gene families involved in calcium signaling have been detected in plants, including calmodulin (CaM), calcium dependent protein kinases (CDPK), calcineurin B-like (CBL) and cyclic nucleotide-gated channels (CNGCs). In our previous study, we demonstrated that Bacillus amyloliquefaciens LZ04 (B. amyloliquefaciens LZ04) regulate genes involved in calcium stress in Arabidopsis thaliana (A. thaliana). Here, we aimed to explore the potential involvement of calcium-related gene families in the response of A. thaliana to calcium stress and the potential regulatory effects of B. amyloliquefaciens LZ04 on these genes. The structure, duplication, synteny, and expression profiles of 102 genes in calcium-related gene families in A. thaliana were investigated. Hidden Markov Models (HMMs) and BLASTP were used to predict candidate genes and conserved domains of the candidate genes were confirmed in SMART and NCBI CDD databases. Gene duplications and synteny were uncovered by BLASTP and phylogenetic analysis. The transcriptome expression profiles of candidate genes were investigated by strand-specific sequencing. Cluster analysis was used to find the expression profiles of calcium-related genes families under different treatment conditions. A total of 102 genes in calcium-related gene families were detected in A. thaliana genome, including 34 CDPK genes, 20 CNGC genes, 18 CIPK genes, 22 IQD genes, and 10 CBP genes. Additionally, of the 102 genes, 33 duplications (32.35%) and 26 gene pairs including 48 genes (47.06%) were detected. Treatment with B. amyloliquefaciens LZ04 enhanced the resistance of A. thaliana under high calcium stress by regulating some of the genes in the calcium-related gene families. Functional enrichment analysis revealed that the genes clustered in the 42nd expression profile which may be B. amyloliquefaciens-responsive genes under calcium stress were enriched in protein phosphorylation and protein modification process. Transcriptome data was validated by RT-PCR and the results generally corroborated the transcriptome sequencing results. These results may be useful for agricultural improvement in high calcium stress regions.

8.
Neurochem Int ; 149: 105122, 2021 10.
Artigo em Inglês | MEDLINE | ID: mdl-34284076

RESUMO

As a double-stranded DNA (dsDNA) sensor, the PYHIN family member absent in melanoma 2 (AIM2) is an essential component of the inflammasome families. Activation of AIM2 by dsDNA leads to the assembly of cytosolic multimolecular complexes termed the AIM2 inflammasome, resulting in activation of caspase-1, the maturation and secretion of pro-inflammatory cytokines interleukin (IL)-1ß and IL-18, and pyroptosis. Multiple central nervous system (CNS) diseases are accompanied by immune responses and inflammatory cascade. As the resident macrophage cells, microglia cells act as the first and main form of active immune defense in the CNS. AIM2 is highly expressed in microglia as well as astrocytes and neurons and is essential in neurodevelopment. In this review, we highlight the recent progress on the role of AIM2 inflammasome in CNS disorders, including cerebral stroke, brain injury, neuropsychiatric disease, neurodegenerative diseases, and glioblastoma.

9.
J Phys Chem Lett ; 12(28): 6448-6456, 2021 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-34236872

RESUMO

Hydroxide ion is a common electrolyte when electrode reactions take place in alkaline media. In the case of oxygen reduction reaction on Pt(111), we demonstrate by ab initio molecular dynamics calculations that the desorption of hydroxyl (OH*) from the electrode surface to form a solvated OH- is a cross-sphere process, with the OH* reactant in the inner sphere and the OH- product directly generated in the aqueous outer sphere. Such a mechanism is distinct from the typical inner sphere and outer sphere reactions. It is dictated by the strong hydrogen bonding interactions between a hydroxide ion and water molecules and is facilitated by proton transfer through solvation layers. It should play a significant role whenever OH* desorption, or its reverse, OH- adsorption, is involved in an electrochemical reaction.

10.
Front Genet ; 12: 670746, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34306014

RESUMO

The tumor microenvironment (TME) has a crucial role in tumor development, progression, and treatment response. Yet, the exact interaction between cancer biology and the TME is not fully understood. The following study analyzed the correlation between immune/stromal/estimate scores and survival prognosis in head and neck squamous cell carcinoma (HNSC) using a bioinformatic method. As a result, a predictive biomarker, UDP-glucose-specific G(i) protein-coupled P2Y receptor (P2RY14), was discovered. The potential role of P2RY14-driven signaling pathways in the immune-remodeling of TME was then investigated. Briefly, low immune scores were associated with unfavorable prognosis and clinical-stage, larger tumor size, and the down-regulation of P2RY14 in HNSC patients. In addition, the survival analysis showed that HNSC patients with high expression had longer survival than patients with low expression from both TCGA databases and our own patients. We further discovered that P2RY14 is involved in the immune activity in the TME of HNSC; a downregulation of P2RY14 resulted in being an indicator for the conversion of TME status (from immune-dominant to metabolic-dominant status). The intersection analysis of genes co-expressed with P2RY14 indicated that the T-cell receptor signaling pathway and PD-L1 expression and PD-1 checkpoint pathway were candidate signaling pathways driven by the P2RY14 gene in HNSC. Further investigation of immune-associated signaling pathways regulated by P2RY14 may help HNSC patients gain higher immunotherapy benefits.

11.
Psychopharmacology (Berl) ; 238(9): 2535-2542, 2021 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-34189597

RESUMO

RATIONALE: Forgetting of fear memory is a current medical therapy for posttraumatic stress disorder (PTSD), and hippocampal long-term depression (LTD) may be the underlying mechanism. Neuregulin 1 (NRG1), a trophic factor, reportedly modulates memory consolidation and synaptic plasticity. METHODS: Fear memory was assessed using contextual fear conditioning. Electrophysiology was used to measure LTD and GABAergic transmission in the hippocampus. OBJECTIVES: To determine the contribution of hippocampal NRG1 to fear memory forgetting and low-frequency stimulation (LFS)-induced LTD. RESULTS: Administration of NRG1 in the hippocampus accelerated forgetting of contextual fear memories. Furthermore, NRG1 had no effect on low-frequency stimulation-induced LTD in young mice but significantly facilitated the induction of LTD and GABAergic transmission in adult animals. More importantly, NRG1-facilitated LTD induction in adult mice could be blocked by inhibition of GABAA receptors and NMDAR activation. CONCLUSION: These findings suggest a role for NRG1 in fear memory forgetting and hippocampal LTD, providing a potential target for the development of drug-assisted PTSD therapy.


Assuntos
Depressão , Neuregulina-1 , Animais , Medo , Hipocampo , Depressão Sináptica de Longo Prazo , Camundongos , Plasticidade Neuronal
12.
J Am Chem Soc ; 143(20): 7868-7875, 2021 05 26.
Artigo em Inglês | MEDLINE | ID: mdl-33974798

RESUMO

The first synthesis of highly strained spirocyclobutane-pyrrolines via a palladium-catalyzed tandem Narasaka-Heck/C(sp3 or sp2)-H activation reaction is reported here. The key step in this transformation is the activation of a δ-C-H bond via an in situ generated σ-alkyl-Pd(II) species to form a five-membered spiro-palladacycle intermediate. The concerted metalation-deprotonation (CMD) process, rate-determining step, and energy barrier of the entire reaction were explored by density functional theory (DFT) calculations. Moreover, a series of control experiments was conducted to probe the rate-determining step and reversibility of the C(sp3)-H activation step.

13.
Org Lett ; 23(11): 4311-4316, 2021 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-33989000

RESUMO

This Letter describes a Pd-catalyzed Tsuji-Trost-type/Heck reaction with allyloxy-tethered aryl iodides and aziridines. The strategy provides efficient access to benzannulated medium-sized rings via intermolecular cyclization. The substrate aryl iodide has two oxidative addition sites, that is, the aromatic C-I bond and the allyl-oxygen bond. The chemoselective oxidative addition of allyl-oxygen bonds is favored, followed by the activation of aromatic C-I bonds. Aziridine plays a key role. Mechanistic studies shed light on the reaction pathway.

14.
Front Pharmacol ; 12: 632767, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33815113

RESUMO

Magnolol (MG) is one of the primary active components of Magnoliae officinalis cortex, which has been widely used in traditional Chinese and Japanese herbal medicine and possesses a wide range of pharmacological activities. In recent years, attention has been drawn to this component due to its potential as an anti-inflammatory and antitumor drug. To summarize the new biological and pharmacological data on MG, we screened the literature from January 2011 to October 2020. In this review, we provide an actualization of already known anti-inflammatory, cardiovascular protection, antiangiogenesis, antidiabetes, hypoglycemic, antioxidation, neuroprotection, gastrointestinal protection, and antibacterial activities of MG. Besides, results from studies on antitumor activity are presented. We also summarized the molecular mechanisms, toxicity, bioavailability, and formulations of MG. Therefore, we provide a valid cognition of MG.

15.
J Org Chem ; 86(8): 5546-5551, 2021 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-33825476

RESUMO

The successful enlargement of the curved π-electron periphery of the wizard hat-shaped polycyclic aromatic compound 1 is described. The target structure 2 features an m,m,p,m,m,p,m,m,p-nonaphenylene belt fused to a central tribenzotriquinacene unit. The synthesis involves a multiple regioconvergent Scholl-type dehydrocyclization as the key step. Spectroscopic, structural, and electronic properties of the title compound 2 are reported.

16.
Org Lett ; 23(7): 2693-2698, 2021 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-33739843

RESUMO

A novel dehydrogenative coupling reaction of N-fluorocarboxamides with polyfluoroarenes forming C(sp2)-C(sp3) bonds enabled by copper catalysis has been accomplished. N-Fluorocarboxamides are postulated to undergo copper-mediated dehydrogenative cross-coupling reaction with electron-deficient polyfluoroarenes via a radical pathway. Benzylic C-H bonds and aliphatic C-H bonds in N-fluorocarboxamides could proceed smoothly and demonstrated excellent regioselectivity. The detailed mechanism presented is supported by control experiments and density functional theory calculations.

17.
Phys Rev Lett ; 126(7): 077001, 2021 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-33666461

RESUMO

A liquid of superconducting vortices generates a transverse thermoelectric response. This Nernst signal has a tail deep in the normal state due to superconducting fluctuations. Here, we present a study of the Nernst effect in two-dimensional heterostructures of Nb-doped strontium titanate (STO) and in amorphous MoGe. The Nernst signal generated by ephemeral Cooper pairs above the critical temperature has the magnitude expected by theory in STO. On the other hand, the peak amplitude of the vortex Nernst signal below T_{c} is comparable in both and in numerous other superconductors despite the large distribution of the critical temperature and the critical magnetic fields. In four superconductors belonging to different families, the maximum Nernst signal corresponds to an entropy per vortex per layer of ≈k_{B}ln2.

18.
Oncoimmunology ; 10(1): 1868122, 2021 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-33537172

RESUMO

Recent advances in immunotherapy, as a part of the multidisciplinary therapy, has gradually gained more attention. However, only a small proportion of patients who sensitive to the therapy could gain benefits. An increasing number of studies indicate that intestinal microbiota could enhance the efficiency of cancer immunotherapy. As one of the main probiotics, Bifidobacterium plays an important role in immune regulation, which has been proved by animal research and human clinical study. But the detailed mechanism was not clearly elucidated. Here we found oral administration of Bifidobacterium breve (B. breve) lw01 could significantly inhibit tumor growth and up-regulate tumor cell apoptosis, which relied on the recruitment of tumor-infiltrating lymphocytes and dendritic cells (DCs) in tumor microenvironment, but not Lactobacillus rhamnosus (L. rhamnosus) CGMCC 1.3724 or Escherichia coli (E. coli) MG1655. In the in situ ligated intestine loop model, B. breve's stimulation triggered the upregulated expression of DC-related chemokine CCL20 and recruited more DCs in the intestinal villi. Further study revealed the enhancement of interleukin 12 (IL-12) secretion derived from DCs is essential to B. breve's antitumor effect, which was counteracted by the treatment of neutralizing antibody for IL-12. Meanwhile, the modulation of intestinal microbiota caused by exogenous B. breve might enhance its antitumor effect. This study provides a simple and easy way to promote antitumor immunity via B. breve.


Assuntos
Bifidobacterium breve , Interleucina-12 , Administração Oral , Animais , Células Dendríticas , Escherichia coli , Humanos
19.
Org Lett ; 22(21): 8267-8271, 2020 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-33048560

RESUMO

This paper describes the case of a cross study between the C-N bond cleavage reaction field and the Catellani-Lautens reaction system. A series of highly functionalized C4-substituted indoles were synthesized using this strategy. By screening the alkyl groups of amines, the energy barrier of C-N bond cleavage reaction was reduced and the corresponding allenization products were avoided. Finally, the density functional theory calculation shows that the inert C-N bond activation reaction is not a concerted process; on the contrary, the coupling reaction first generates indole quaternary ammonium salt, and then C-N bond cleavage occurs via an SN2 process.

20.
Phys Chem Chem Phys ; 22(39): 22226-22235, 2020 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-32996982

RESUMO

For the oxygen reduction reaction (ORR) in acidic media, a proton is a key component in the hydrogenation of O2, O, and OH. Modeling a proton requires an explicit account of its solvation and its dynamic nature in the interfacial solution region. We employed ab initio molecular dynamics to study these reactions on Pt(111), which is a model problem in electro-catalysis. Our results show that the branching ratio for the two hydrogenation channels of O atoms adsorbed on Pt(111) shifts dramatically with the electrode potential. This kinetic factor underlies the electrochemical observations peculiar to ORR on Pt(111) and provides an explanation for the long-standing puzzle of its high onset overpotential.

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