278 research outputs found
Tetranuclear coordination assemblies based on half-sandwich ruthenium(II) complexes. Non covalent binding to DNA and cytotoxicity.
The reaction of [(cymene)RuCl2]2 with K2Hoxonate (H3oxonic = 4,6-dihydroxy-2-carboxy-1,3,5-triazine acid) in methanol leads to the formation of the dinuclear half-sandwich ruthenium(II) complex [(cymene)2Ru2(\u3bc-Hoxonato)Cl2] (1a). Removal of the chloride ligands of 1a by treatment with AgCF3SO3 yields [(cymene)2Ru2(\u3bc-Hoxonato)(CF3SO3)2] (1b), which, upon posterior reaction with N,N'-linkers (L = 4,4'-bipyridine (4,4'-bpy), 4,7-phenantroline (4,7-phen)), gives rise to the formation of the tetranuclear open boxes [(cymene)4Ru4(\u3bc-Hoxonato)2(\u3bc-N,N'-L)2](CF3SO3)4 (2a, L = 4,4'-bpy; 2b, L = 4,7-phen). These systems have been characterized by 1HNMR, UV-vis, and ESI-MS. The single-crystal structures of the dinuclear precursor 1a and of the clathrate 2b 824,7-phen have been determined. The interaction of these systems with cysteine, mononucleotides, and calf-thymus DNA has been studied by means of 1HNMR, UV-vis, circular dicroism, competitive binding assays, and atomic force microscopy imaging. The results show that the robust tetracationic ruthenium(II) cyclic systems 2a and 2b do not give ligand exchange reactions toward biorelevant ligands. Nevertheless, these systems are able to noncovalently bind to DNA, probably at the surface of the major groove, inducing significant conformational changes in this biomolecule. It is also interesting to note that compounds 2a and 2b, in spite of only giving supramolecular interactions with biomolecules, exhibit antitumor activity, particularly toward the human ovarian cancer cell line A2780cisR, showing acquired resistance to cisplatin, with respective 4.6 and 8.3 microM IC50 values
Crystalline fibres of a covalent organic framework through bottom-up microfluidic synthesis
A microfluidic chip has been used to prepare fibres of a porous polymer with high structural order, setting a precedent for the generation of a wide variety of materials using this reagent mixing approach that provides unique materials not accessible easily through bulk processes. The reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde in acetic acid under continuous microfluidic flow conditions leads to the formation of a highly crystalline and porous covalent organic framework (hereafter denoted as MF-COF-1), consisting of fibrillar micro-structures, which have mechanical stability that allows for direct drawing of objects on a surfaceFinancial support from Spanish Government (Projects MAT2013-46753-C2-1-P and CTQ2014-53486-R) and FEDER are acknowledged. A. A. and J. P. L. would like to thank the financial support from the Swiss National Science Foundation (SNSF) through the project no. 200021_16017
Scalable Synthesis and Electrocatalytic Performance of Highly Fluorinated Covalent Organic Frameworks for Oxygen Reduction
In this study, we present a novel approach for the synthesis of covalent organic frameworks (COFs) that overcomes the common limitations of non-scalable solvothermal procedures. Our method allows for the room-temperature and scalable synthesis of a highly fluorinated DFTAPB-TFTA-COF, which exhibits intrinsic hydrophobicity. We used DFT-based calculations to elucidate the role of the fluorine atoms in enhancing the crystallinity of the material through corrugation effects, resulting in maximized interlayer interactions, as disclosed both from PXRD structural resolution and theoretical simulations. We further investigated the electrocatalytic properties of this material towards the oxygen reduction reaction (ORR). Our results show that the fluorinated COF produces hydrogen peroxide selectively with low overpotential (0.062 V) and high turnover frequency (0.0757 sâ1) without the addition of any conductive additives. These values are among the best reported for non-pyrolyzed and metal-free electrocatalysts. Finally, we employed DFT-based calculations to analyse the reaction mechanism, highlighting the crucial role of the fluorine atom in the active site assembly. Our findings shed light on the potential of fluorinated COFs as promising electrocatalysts for the ORR, as well as their potential applications in other fieldsThis work was financially supported by Ministerio de Ciencia e InnovaciĂłn of Spain MICINN (TED2021-129886B-C41, TED2021-129886BC42; TED2021-129886BC43; PID2019-106268GB-C32; PID2019-106268GB C33, PID2020-113608RB-I00; PID2022-138908NB-C33, PID2022-138470NB-100, RED2018-102412-T; PID2020-116728RB-I00). Comunidad de Madrid (P2018/NMT-4349 TRANSNANOAVANSENS Program; SI3/PJI/2021-0034). F.Z. acknowledge financial support from the Spanish Ministry of Science and Innovation, through the âMarĂa de Maeztuâ Programme for Units of Excellence in R&D (CEX2018-000805-M). R.V. acknowledges âPrograma Juan de la Cierva FormaciĂłnâ (FJC2020-045043-I). R.V. and
J.A.R.N. acknowledge MCIN/AEI/10.13039/501100011033 and European Union NextGenerationEU/PRTR
Chlorination of a Zeolitic-Imidazolate Framework Tunes Packing and van der Waals Interaction of Carbon Dioxide for Optimized Adsorptive Separation
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.0c08942.L.H.W. acknowledges the Fonds Wetenschappelijk Onderzoek
(FWO) - Vlaanderen for a senior postdoctoral research
fellowship and International Mobility fellowship under
contract numbers of 12M1418N and V402319N, respectively.
S.V.D.B., S.M.J.R., and J.W. acknowledge Fonds Wetenschappelijk
Onderzoek (FWO) - Vlaanderen for Grants 11U1914N,
12T3519N, and 1103618N as well as the Research Board of
Ghent University (BOF). J.A.R.N. acknowledges generous
funding from the Spanish Ministry of Economy (CTQ2014-
53486-R) and FEDER from the European Union. Funding was
also received from the European Unionâs Horizon 2020
Research and Innovation Programme [ERC Consolidator
Grant Agreement 647755 - DYNPOR (2015â2020)]. J.A.M.
and C.E.A.K. gratefully acknowledge financial support from the
Flemish Government (Long-term structural funding Methusalem
and FWO support). Collaboration among universities was
supported by the Belgian Government (IAP-PAI network).Molecular separation of carbon dioxide (CO2) and methane (CH4) is of growing interest for biogas upgrading, carbon capture and utilization, methane synthesis and for purification of natural gas. Here, we report a new zeolitic-imidazolate framework (ZIF), coined COK-17, with exceptionally high affinity for the adsorption of CO2 by London dispersion forces, mediated by chlorine substituents of the imidazolate linkers. COK-17 is a new type of flexible zeolitic-imidazolate framework Zn(4,5-dichloroimidazolate)(2) with the SOD framework topology. Below 200 K it displays a metastable closed-pore phase next to its stable open-pore phase. At temperatures above 200 K, COK-17 always adopts its open-pore structure, providing unique adsorption sites for selective CO2 adsorption and packing through van der Waals interactions with the chlorine groups, lining the walls of the micropores. Localization of the adsorbed CO2 molecules by Rietveld refinement of X-ray diffraction data and periodic density functional theory calculations revealed the presence and nature of different adsorption sites. In agreement with experimental data, grand canonical Monte Carlo simulations of adsorption isotherms of CO2 and CH4 in COK-17 confirmed the role of the chlorine functions of the linkers and demonstrated the superiority of COK-17 compared to other adsorbents such as ZIF-8 and ZIF-71.FWO
12M1418N
V402319N
11U1914N
12T3519N
1103618NSpanish Ministry of Economy
CTQ201453486-RFEDER from the European UnionEuropean Union's Horizon 2020 Research and Innovation Programme [ERC]
647755 - DYNPORFlemish Government (Long-term structural funding Methusalem)FWOBelgian Government (IAP-PAI network
kokusui shugisha no kokusai ninshiki to kokka koso :fukumoto nichinan o chushin to shite
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Ionic Conductivity and Potential Application for Fuel Cell of a Modified Imine-Based Covalent Organic Framework
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, © American Chemical Society after peer review and technical editing by the publisher.
To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/jacs.7b05182We present the novel potential application of imine-based covalent organic frameworks (COFs), formed by the direct Schiff reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde building blocks in m-cresol or acetic acid, named RT-COF-1 or RT-COF-1Ac/RT-COF-1AcB. The post-synthetic treatment of RT-COF-1 with LiCl leads to the formation of LiCl@RT-COF-1. The ionic conductivity of this series of polyimine COFs has been characterized at variable temperature and humidity, using electrochemical impedance spectroscopy. LiCl@RT-COF-1 exhibits a conductivity value of 6.45 Ă 10-3 S cm-1 (at 313 K and 100% relative humidity) which is among the highest values so far reported in proton conduction for COFs. The mechanism of conduction has been determined using 1H and 7Li solid-state nuclear magnetic resonance spectroscopy. Interestingly, these materials, in the presence of controlled amounts of acetic acid and under pressure, show a remarkable processability that gives rise to quasi-transparent and flexible films showing in-plane structural order as confirmed by X-ray crystallography. Finally, we prove that these films are useful for the construction of proton exchange membrane fuel cells (PEMFC) reaching values up to 12.95 mW cm-2 and 53.1 mA cm-2 for maximum power and current density at 323 K, respectivelyWe thank the MINECO (Spain) for financial support through Juan de la Cierva postdoctoral fellowship. We thank the Spanish Ministry of Economy (MAT2016-77608-C3-1-P,
MAT2013-46753-C2-1-P, CTQ2014-53486-R, ENE2016-77055-C3-1-R), and Comunidad de Madrid (S2013/MAE2882) for generous fundin
Search for direct production of charginos and neutralinos in events with three leptons and missing transverse momentum in âs = 7 TeV pp collisions with the ATLAS detector
A search for the direct production of charginos and neutralinos in final states with three electrons or muons and missing transverse momentum is presented. The analysis is based on 4.7 fbâ1 of protonâproton collision data delivered by the Large Hadron Collider and recorded with the ATLAS detector. Observations are consistent with Standard Model expectations in three signal regions that are either depleted or enriched in Z-boson decays. Upper limits at 95% confidence level are set in R-parity conserving phenomenological minimal supersymmetric models and in simplified models, significantly extending previous results
Jet size dependence of single jet suppression in lead-lead collisions at sqrt(s(NN)) = 2.76 TeV with the ATLAS detector at the LHC
Measurements of inclusive jet suppression in heavy ion collisions at the LHC
provide direct sensitivity to the physics of jet quenching. In a sample of
lead-lead collisions at sqrt(s) = 2.76 TeV corresponding to an integrated
luminosity of approximately 7 inverse microbarns, ATLAS has measured jets with
a calorimeter over the pseudorapidity interval |eta| < 2.1 and over the
transverse momentum range 38 < pT < 210 GeV. Jets were reconstructed using the
anti-kt algorithm with values for the distance parameter that determines the
nominal jet radius of R = 0.2, 0.3, 0.4 and 0.5. The centrality dependence of
the jet yield is characterized by the jet "central-to-peripheral ratio," Rcp.
Jet production is found to be suppressed by approximately a factor of two in
the 10% most central collisions relative to peripheral collisions. Rcp varies
smoothly with centrality as characterized by the number of participating
nucleons. The observed suppression is only weakly dependent on jet radius and
transverse momentum. These results provide the first direct measurement of
inclusive jet suppression in heavy ion collisions and complement previous
measurements of dijet transverse energy imbalance at the LHC.Comment: 15 pages plus author list (30 pages total), 8 figures, 2 tables,
submitted to Physics Letters B. All figures including auxiliary figures are
available at
http://atlas.web.cern.ch/Atlas/GROUPS/PHYSICS/PAPERS/HION-2011-02
Search for displaced vertices arising from decays of new heavy particles in 7 TeV pp collisions at ATLAS
We present the results of a search for new, heavy particles that decay at a
significant distance from their production point into a final state containing
charged hadrons in association with a high-momentum muon. The search is
conducted in a pp-collision data sample with a center-of-mass energy of 7 TeV
and an integrated luminosity of 33 pb^-1 collected in 2010 by the ATLAS
detector operating at the Large Hadron Collider. Production of such particles
is expected in various scenarios of physics beyond the standard model. We
observe no signal and place limits on the production cross-section of
supersymmetric particles in an R-parity-violating scenario as a function of the
neutralino lifetime. Limits are presented for different squark and neutralino
masses, enabling extension of the limits to a variety of other models.Comment: 8 pages plus author list (20 pages total), 8 figures, 1 table, final
version to appear in Physics Letters
Measurement of the polarisation of W bosons produced with large transverse momentum in pp collisions at sqrt(s) = 7 TeV with the ATLAS experiment
This paper describes an analysis of the angular distribution of W->enu and
W->munu decays, using data from pp collisions at sqrt(s) = 7 TeV recorded with
the ATLAS detector at the LHC in 2010, corresponding to an integrated
luminosity of about 35 pb^-1. Using the decay lepton transverse momentum and
the missing transverse energy, the W decay angular distribution projected onto
the transverse plane is obtained and analysed in terms of helicity fractions
f0, fL and fR over two ranges of W transverse momentum (ptw): 35 < ptw < 50 GeV
and ptw > 50 GeV. Good agreement is found with theoretical predictions. For ptw
> 50 GeV, the values of f0 and fL-fR, averaged over charge and lepton flavour,
are measured to be : f0 = 0.127 +/- 0.030 +/- 0.108 and fL-fR = 0.252 +/- 0.017
+/- 0.030, where the first uncertainties are statistical, and the second
include all systematic effects.Comment: 19 pages plus author list (34 pages total), 9 figures, 11 tables,
revised author list, matches European Journal of Physics C versio
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