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1.
Artigo em Inglês | MEDLINE | ID: mdl-32515536

RESUMO

Methanation of carbon dioxide (CO2 ) is attractive within the context of a renewable energy refinery. Herein, we report an indirect methanation method that harnesses amino alcohols as relay molecules in combination with a catalyst comprising ruthenium nanoparticles (NPs) immobilized on a Lewis acidic and robust metal-organic framework (MOF). The Ru NPs are well dispersed on the surface of the MOF crystals and have a narrow size distribution. The catalyst efficiently transforms amino alcohols to oxazolidinones (upon reaction with CO2 ) and then to methane (upon reaction with hydrogen), simultaneously regenerating the amino alcohol relay molecule. This protocol provides a sustainable, indirect way for CO2 methanation as the process can be repeated multiple times.

2.
Nano Lett ; 2020 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-32568553

RESUMO

The association between carbon nanotubes (CNTs) and polymers to afford functional composites has been attributed to enthalpic interactions, neglecting the entropic depletion effect, in which bound solvents are released during the association process. Here, we show that association between multiwalled CNTs and common polymers is governed by the depletion effect, generating a corresponding entropic free energy up to ca. 13 kJ mol-1 at room temperature, while the enthalpic contribution is insignificant or even negative. Notably, association between the polymers and the CNTs takes place preferentially at the highly stacked CNT junctions, leading to mechanical reinforcement without impacting conductivity. Consequently, high-performance composite membranes were fabricated from inexpensive multiwalled CNTs and polyacrylonitrile (PAN) and were used as electrode supports for platinum (Pt) nanoparticles, affording specific currents 6-7-fold higher than that of Pt foil in the hydrogen evolution reaction and displaying outstanding stability.

3.
Artigo em Inglês | MEDLINE | ID: mdl-32372095

RESUMO

OBJECTIVES: Malignant pleural mesothelioma (MPM) is a deadly disease with limited treatment options. Approaches to enhance patient immunity against MPM have been tested but shown variable results. Previously, we have demonstrated interesting vascular modulating properties of low-dose photodynamic therapy (L-PDT) on MPM. Here, we hypothesized that L-PDT vascular modulation could favour immune cell extravasation in MPM and improve tumour control in combination with immune checkpoint inhibitors. METHODS: First, we assessed the impact of L-PDT on vascular endothelial E-selectin expression, a key molecule for immune cell extravasation, in vitro and in a syngeneic murine model of MPM. Second, we characterized the tumour immune cell infiltrate by 15-colour flow cytometry analysis 2 and 7 days after L-PDT treatment of the murine MPM model. Third, we determined how L-PDT combined with immune checkpoint inhibitor anti-CTLA4 affected tumour growth in a murine MPM model. RESULTS: L-PDT significantly enhanced E-selectin expression by endothelial cells in vitro and in vivo. This correlated with increased CD8+ T cells and activated antigen-presenting cells (CD11b+ dendritic cells and macrophages) infiltration in MPM. Also, compared to anti-CTLA4 that only affects tumour growth, the combination of L-PDT with anti-CTLA4 caused complete MPM regression in 37.5% of animals. CONCLUSIONS: L-PDT enhances E-selectin expression in the MPM endothelium, which favours immune infiltration of tumours. The combination of L-PDT with immune checkpoint inhibitor anti-CTLA4 allows best tumour control and regression.

4.
J Am Chem Soc ; 2020 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-32391696

RESUMO

The employment of 2D perovskites is a promising approach to tackling the stability and voltage issues inherent in perovskite solar cells. It remains unclear, however, whether other perovskites with different dimensionalities have the same effect on efficiency and stability. Here, we report the use of quasi-3D azetidinium lead iodide (AzPbI3) as a secondary layer on top of the primary 3D perovskite film that results in significant improvements in the photovoltaic parameters. Remarkably, the utilization of AzPbI3 leads to a new passivation mechanism due to the presence of surface dipoles resulting in a power conversion efficiency (PCE) of 22.4%. The open-circuit voltage obtained is as high as 1.18 V, which is among the highest reported to date for single junction perovskite solar cells, corresponding to a voltage deficit of 0.37 V for a band gap of 1.55 eV.

5.
Molecules ; 25(7)2020 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-32260272

RESUMO

A series of diiron/tetrairon compounds containing a S- or a Se-function (2a-d, 4a-d, 5a-b, 6), and the monoiron [FeCp(CO){SeC1(NMe2)C2HC3(Me)}] (3) were prepared from the diiron µ-vinyliminium precursors [Fe2Cp2(CO)( µ-CO){ µ-η1: η3-C3(R')C2HC1N(Me)(R)}]CF3SO3 (R = R' = Me, 1a; R = 2,6-C6H3Me2 = Xyl, R' = Ph, 1b; R = Xyl, R' = CH2OH, 1c), via treatment with S8 or gray selenium. The new compounds were characterized by elemental analysis, IR and multinuclear NMR spectroscopy, and structural aspects were further elucidated by DFT calculations. The unprecedented metallacyclic structure of 3 was ascertained by single crystal X-ray diffraction. The air-stable compounds (3, 4a-d, 5a-b, 6) display fair to good stability in aqueous media, and thus were assessed for their cytotoxic activity towards A2780, A2780cisR, and HEK-293 cell lines. Cyclic voltammetry, ROS production and NADH oxidation studies were carried out on selected compounds to give insights into their mode of action.

7.
Angew Chem Int Ed Engl ; 59(19): 7501-7507, 2020 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-32049401

RESUMO

Core-shell nanocatalysts are attractive due to their versatility and stability. Here, we describe cobalt nanoparticles encapsulated within graphitic shells prepared via the pyrolysis of a cationic poly-ionic liquid (PIL) with a cobalt(II) chloride anion. The resulting material has a core-shell structure that displays excellent activity and selectivity in the self-dehydrogenation and hetero-dehydrogenation of primary amines to their corresponding imines. Furthermore, the catalyst exhibits excellent activity in the synthesis of secondary imines from substrates with various reducible functional groups (C=C, C≡C and C≡N) and amino acid derivatives.

8.
ChemSusChem ; 13(8): 2025-2031, 2020 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-31994287

RESUMO

The metal- and solvent-free capture and reduction of large amounts of CO2 to formate under ambient conditions is achieved by combining a pyrrolidinium-based ionic liquid with a borohydride anion. This material demonstrates one of the highest CO2 capacities at room temperature and 1 bar with up to 1 g CO 2 g-1 IL . CO2 gas reacts with the BH4 - anion to give triformatoborohydride, [HB(OCHO)3 ]- . The reaction occurs without loss in capacity at low CO2 concentration (6 vol % diluted with N2 ). The thermodynamics and kinetics of the reaction were monitored by using a magnetic suspended balance. In addition, more than 1 mol CO 2 mol-1 [ EMPY ] [ BH 4 ] is captured and reduced if air is used as a CO2 source. The product can be then treated with HCl to give formic acid and the corresponding ionic liquid chloride, which can be recycled. This ionic liquid borohydride demonstrates great potential as a CO2 absorber and reducer to produce alternative fuels.

9.
Angew Chem Int Ed Engl ; 59(3): 1002-1017, 2020 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-31364789

RESUMO

Organocatalysts promote a range of C-N bond forming reactions of amines with CO2 . Herein, we review these reactions and attempt to identify the unifying features of the catalysts that allows them to promote a multitude of seemingly unrelated reactions. Analysis of the literature shows that these reactions predominantly proceed by carbamate salt formation in the form [BaseH][RR'NCOO]. The anion of the carbamate salt acts as a nucleophile in hydrosilane reductions of CO2 , internal cyclization reactions or after dehydration as an electrophile in the synthesis of urea derivatives. The reactions are enhanced by polar aprotic solvents and can be either promoted or hindered by H-bonding interactions. The predominant role of all types of organic and salt catalysts (including ionic liquids, ILs) is the stabilization of the carbamate salt, mostly by acting as a base. Catalytic enhancement depends on the combination of the amine, the base strength, the solvent, steric factors, ion pairing and H-bonding. A linear relationship between the base strength and the reaction yield has been demonstrated with IL catalysts in the synthesis of formamides and quinazoline-2,4-diones. The role of organocatalysts in the reactions indicates that all bases of sufficient strength should be able to catalyze the reactions. However, a physical limit to the extent of a purely base catalyzed reaction mechanism should exist, which needs to be identified, understood and overcome by synergistic or alternative methods.

10.
Arch Insect Biochem Physiol ; 103(3): e21645, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31742774

RESUMO

In insect reverse genetics, dietary delivery of interfering RNAs is a practical approach in nonmodel species, such as thrips, whose small size, and feeding behavior restricts the use of other delivery methods. In a laboratory context, an unsuitable diet could confound the interpretation of an RNA interference (RNAi) phenotype, however well-formulated artificial diets can minimize experimental variability, reduce the need for insect handling, and can further be used for roles, such as delivering double-strand RNA (dsRNA)-expressing recombinant bacteria. In this study, artificial diets for oral delivery of dsRNA were developed for two important pest thrips species, western flower thrips (Frankliniella occidentalis) and onion thrips (Thrips tabaci), with the goal of (a) stimulating feeding behavior, (b) supporting optimal growth rates of dsRNA-expressing symbiotic bacteria, and (c) nutritionally supporting the thrips for sufficient periods to observe RNAi phenotypes. The efficacy of artificial diets for ingesting "naked" dsRNA or dsRNA-expressing symbionts and dsRNA delivery via host plant uptake was evaluated. Compared with previously published diet formulations, new combinations based on tryptone, yeast, and soy were superior for enhancing feeding and longevity. However, simply adding "naked" dsRNA to an artificial diet was an unreliable form of RNAi delivery in our hands due to dsRNA degradation. Delivery via host plants was more successful, and the new diet formulation was suitable for symbiont-mediated dsRNA delivery, which we believe is the most convenient approach for large-scale knockdown experiments. This study, therefore, provides alternative methodologies for thrips rearing, dietary RNAi delivery, and insights into the challenges of performing dietary RNAi in nonmodel insects.


Assuntos
Comportamento Alimentar , Controle de Insetos/métodos , Controle Biológico de Vetores/métodos , Interferência de RNA , Tisanópteros , Animais , Bactérias , Insetos Vetores , RNA de Cadeia Dupla
11.
Curr Opin Chem Biol ; 56: 28-34, 2019 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-31812831

RESUMO

From their early successes in medicine, organometallic compounds continue to attract interest as potential chemotherapeutics to treat a range of diseases. Here, we show from recent literature selected largely from the last two years that organometallics offer unique opportunities in medicine and, increasingly, a mechanistic-based approach is applied to their development, which has not always been the case.

12.
Int J Mol Sci ; 20(21)2019 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-31694163

RESUMO

Lysozyme is one of the most important anti-bacterial effectors in the innate immune system of animals. Besides its direct antibacterial enzymatic activity, lysozyme displays other biological properties, pointing toward a significant anti-inflammatory effect, many aspects of which are still elusive. Here we investigate the perturbation of gene expression profiles induced by lysozyme in a monocyte cell line in vitro considering a perspective as broad as the whole transcriptome profiling. The results of the RNA-seq experiment show that lysozyme induces transcriptional modulation of the TNF-α/IL-1ß pathway genes in U937 monocytes. The analysis of transcriptomic profiles with IPA® identified a simple but robust molecular network of genes, in which the regulation trends are fully consistent with the anti-inflammatory activity of lysozyme. This study provides the first evidence in support of the anti-inflammatory action of lysozyme on the basis of transcriptomic regulation data resulting from the broad perspective of a whole-transcriptome profiling. Such important effects can be achieved with the supplementation of relatively low concentrations of lysozyme, for a short time of exposure. These new insights allow the potential of lysozyme in pharmacological applications to be better exploited.


Assuntos
Monócitos/imunologia , Muramidase/imunologia , Ativação Transcricional , Transcriptoma , Fator de Necrose Tumoral alfa/genética , Linhagem Celular , Humanos , Inflamação/genética , Inflamação/imunologia , Interleucina-1beta/genética , Interleucina-1beta/imunologia , Monócitos/metabolismo , Transdução de Sinais , Fator de Necrose Tumoral alfa/imunologia
13.
Chemistry ; 25(65): 14739, 2019 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-31755609

RESUMO

Invited for the cover of this issue is the group of Fabio Marchetti at the Università di Pisa and Paul J. Dyson at Ecole Polytechnique Fédérale de Lausanne (EPFL). Read the full text of the article at 10.1002/chem.201902885.

14.
Chem Commun (Camb) ; 55(87): 13089-13092, 2019 Oct 29.
Artigo em Inglês | MEDLINE | ID: mdl-31608908

RESUMO

The tandem synthesis of benzimidazole and other azoles can be achived by the N-formylation of ortho-substituted anilines followed by a cyclization reaction. However, CO2-based N-formylations with hydrosilane reducing agents are base catalyzed whereas the cyclization reaction is acid catalyzed. The mismatch in catalytic conditions means that only one of the steps can be catalyzed in a single pot reaction. While the N-formylation reaction is frequently the target of catalyst development, the cyclization reaction requires comparably much harsher reaction conditions. Identification of these difficulties lead us to the development of a one-pot, two-step synthesis of benzimidazole under mild reaction conditions employing acid catalysts.

15.
Angew Chem Int Ed Engl ; 58(44): 15660-15664, 2019 10 28.
Artigo em Inglês | MEDLINE | ID: mdl-31478581

RESUMO

Targeting defined histone protein sites in chromatin is an emerging therapeutic approach that can potentially be enhanced by allosteric effects within the nucleosome. Here we characterized a novel hetero-bimetallic compound with a design based on a nucleosomal allostery effect observed earlier for two unrelated drugs-the RuII antimetastasis/antitumor RAPTA-T and the AuI anti-arthritic auranofin. The RuII moiety binds specifically to two H2A glutamate residues on the nucleosome acidic patch, allosterically triggering a cascade of structural changes that promote binding of the AuI moiety to selective histidine residues on H3, resulting in cross-linking sites that are over 35 Šdistant. By tethering the H2A-H2B dimers to the H3-H4 tetramer, the hetero-bimetallic compound significantly increases stability of the nucleosome, illustrating its utility as a site-selective cross-linking agent.

16.
ACS Appl Mater Interfaces ; 11(34): 31311-31316, 2019 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-31369232

RESUMO

Natural polymers such as those present in foods contain abundant noncovalent intra- and intermolecular interactions, notably hydrogen bonds, which make them rigid when dry, but on exposure to water soften, due to disruption of these interactions. This softening process allows them to be reshaped. Food-derived materials, however, have limited practical use due to their high brittleness and gradual degradation. Nevertheless, inspired by such properties, surfactant-polyelectrolyte-based polymers that contain abundant ionic interactions and can be repeatedly reshaped using water as plasticizer are described. The polymers, on the basis of main chain anionic poly(styrene sulfonates) combined with phosphonium surfactant, are readily synthesized with well-defined lamellar domains through interfacial metathesis reactions. The polymers present typical stress-strain characteristics of plastics, and their modulus undergoes a decrease of ca. 3 orders of magnitude upon shear and stretch forces after plasticizing with water. Since recycling of plastics generally involves complicated and energy-intensive processes (that leads to the majority of plastics being land-filled or incinerated), it is envisaged that reshapable polymers, such as those described here, could reduce the amount of plastic waste as they can be remolded as and when required, thus reducing pollution and the depletion of resources, ultimately contributing to a more sustainable society.

17.
Chemistry ; 25(65): 14801-14816, 2019 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-31441186

RESUMO

Although ferrocene derivatives have attracted considerable attention as possible anticancer agents, the medicinal potential of diiron complexes has remained largely unexplored. Herein, we describe the straightforward multigram-scale synthesis and the antiproliferative activity of a series of diiron cyclopentadienyl complexes containing bridging vinyliminium ligands. IC50 values in the low-to-mid micromolar range were determined against cisplatin sensitive and resistant human ovarian carcinoma (A2780 and A2780cisR) cell lines. Notable selectivity towards the cancerous cells lines compared to the non-tumoral human embryonic kidney (HEK-293) cell line was observed for selected compounds. The activity seems to be multimodal, involving reactive oxygen species (ROS) generation and, in some cases, a fragmentation process to afford monoiron derivatives. The large structural variability, amphiphilic character and good stability in aqueous media of the diiron vinyliminium complexes provide favorable properties compared to other widely studied classes of iron-based anticancer candidates.

18.
Chem Commun (Camb) ; 55(73): 10964-10967, 2019 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-31451825

RESUMO

Finding pragmatic solutions to curb the accumulation of atmospheric CO2 and tackle the associated greenhouse effect is challenging. Herein, we demonstrate the use of an in situ formed frustrated Lewis pair (FLP) within a metal-organic framework (MOF) to effectively hydrogenate CO2 to methoxide at a relatively low temperature and pressure. The work presents a step toward the discovery of practical catalysts for CO2 reduction and conversion.

19.
Angew Chem Int Ed Engl ; 58(33): 11266-11272, 2019 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-31165529

RESUMO

The synthesis of three enamine hole-transporting materials (HTMs) based on Tröger's base scaffold are reported. These compounds are obtained in a three-step facile synthesis from commercially available materials without the need of expensive catalysts, inert conditions or time-consuming purification steps. The best performing material, HTM3, demonstrated 18.62 % PCE in PSCs, rivaling spiro-OMeTAD in efficiency, and showing markedly superior long-term stability in non-encapsulated devices. In dopant-free PSCs, HTM3 outperformed spiro-OMeTAD by a factror of 1.6. The high glass-transition temperature (Tg =176 °C) of HTM3 also suggests promising perspectives in device applications.

20.
Prog Retin Eye Res ; 73: 100764, 2019 11.
Artigo em Inglês | MEDLINE | ID: mdl-31173880

RESUMO

Retinoblastoma is lethal by metastasis if left untreated, so the primary goal of therapy is to preserve life, with ocular survival, visual preservation and quality of life as secondary aims. Historically, enucleation was the first successful therapeutic approach to decrease mortality, followed over 100 years ago by the first eye salvage attempts with radiotherapy. This led to the empiric delineation of a window for conservative management subject to a "state of metastatic grace" never to be violated. Over the last two decades, conservative management of retinoblastoma witnessed an impressive acceleration of improvements, culminating in two major paradigm shifts in therapeutic strategy. Firstly, the introduction of systemic chemotherapy and focal treatments in the late 1990s enabled radiotherapy to be progressively abandoned. Around 10 years later, the advent of chemotherapy in situ, with the capitalization of new routes of targeted drug delivery, namely intra-arterial, intravitreal and now intracameral injections, allowed significant increase in eye preservation rate, definitive eradication of radiotherapy and reduction of systemic chemotherapy. Here we intend to review the relevant knowledge susceptible to improve the conservative management of retinoblastoma in compliance with the "state of metastatic grace", with particular attention to (i) reviewing how new imaging modalities impact the frontiers of conservative management, (ii) dissecting retinoblastoma genesis, growth patterns, and intraocular routes of tumor propagation, (iii) assessing major therapeutic changes and trends, (iv) proposing a classification of relapsing retinoblastoma, (v) examining treatable/preventable disease-related or treatment-induced complications, and (vi) appraising new therapeutic targets and concepts, as well as liquid biopsy potentiality.


Assuntos
Antineoplásicos/administração & dosagem , Neoplasias da Retina/tratamento farmacológico , Retinoblastoma/tratamento farmacológico , Comorbidade , Tratamento Conservador , Enucleação Ocular , Humanos , Infusões Intra-Arteriais , Injeções Intravítreas , Recidiva Local de Neoplasia , Qualidade de Vida , Neoplasias da Retina/patologia , Retinoblastoma/secundário , Acuidade Visual/fisiologia
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