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1.
Dr. Silvia Castro-Fernández Carlos M. Cruz Dr. Inês F. A. Mariz Dr. Irene R. Márquez Vicente G. Jiménez Lucía Palomino-Ruiz Prof. Juan M. Cuerva Dr. Ermelinda Maçôas Dr. Araceli G. Campaña 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(18):7205-7211
A new family of distorted ribbon-shaped nanographenes was designed, synthesized, and their optical and electrochemical properties were evaluated, pointing out an unprecedented correlation between their structural characteristics and the two-photon absorption (TPA) responses and electrochemical band gaps. Three nanographene ribbons have been prepared: a seven-membered-ring-containing nanographene presenting a tropone moiety at the edge, its full-carbon analogue, and a purely hexagonal one. We have found that the TPA cross-sections and the electrochemical band gaps of the seven-membered-ring-containing compounds are higher and lower, respectively, than those of the fully hexagonal polycyclic aromatic hydrocarbon (PAH). Interestingly, the inclusion of additional curvature has a positive effect in terms of non-linear optical properties of those ribbons. 相似文献
2.
Maria Ciaccia Irene Tosi Laura Baldini Roberta Cacciapaglia Luigi Mandolini Stefano Di Stefano Christopher A. Hunter 《Chemical science》2015,6(1):144-151
A new strategy for determining thermodynamic effective molarities (EM) for macrocylisation reactions using dynamic combinatorial chemistry under dilute conditions is presented. At low concentrations, below the critical value, Dynamic Libraries (DLs) of bifunctional building blocks contain only cyclic species, so it is not possible to quantify the equilibria between linear and cyclic species. However, addition of a monofunctional chain stopper can be used to promote the formation of linear oligomers allowing measurement of EM for all cyclic species present in the DL. The effectiveness of this approach was demonstrated for DLs generated from mixtures of 1,3-diimine calix[4]arenes, linear diaminoalkanes and monoaminoalkanes. For macrocycles deriving from one bifunctional calixarene and one diamine, there is an alternating pattern of EM values with the number of methylene units in the diamine: odd numbers give significantly higher EMs than even numbers. For odd numbers of methylene units, the alkyl chain can adopt an extended all anti conformation, whereas for even numbers of methylene units, gauche conformations are required for cyclisation, and the associated strain reduces EM. The value of EM for the five-carbon linker indicates that this macrocycle is a strainless ring. 相似文献
3.
4.
Marina Sicignano Dr. Rosaria Schettini Luisa Sica Giovanni Pierri Prof. Dr. Francesco De Riccardis Prof. Dr. Irene Izzo Dr. Bholanath Maity Dr. Yury Minenkov Prof. Dr. Luigi Cavallo Dr. Giorgio Della Sala 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(29):7131-7141
The first highly enantioselective arylogous Michael reaction (AMR) of 3-unsubstituted phthalides has been described. This phase-transfer methodology, which uses catalytic amounts of KOH/18-crown-6 catalyst in mesitylene in the presence of N,O-bis(trimethylsilyl)acetamide (BSA), gives access to a broad range of 3-monosubstituted phthalides with high levels of syn diastereoselectivity and good yields, starting from 3-unsubstituted derivatives and diverse α,β-unsaturated carbonyl compounds. The reaction also applies to unactivated 3-alkyl phthalides to afford 3,3-dialkyl derivatives. A plausible mechanism has been suggested. DFT analysis of possible transition states gives a rationale of the high syn diastereoselectivity observed and its correlation with the solvent's dielectric constant. 相似文献
5.
Rajagopal Karthikeyan Khalaf Abdul Jalil M. Parastesh Fatemeh Moroz Irene Karthikeyan Anitha Jafari Sajad 《Nonlinear dynamics》2019,98(1):477-487
Nonlinear Dynamics - In this paper, the extended Hindmarsh–Rose neuron model, which considers the slow intracellular exchange of calcium ions between its store and the cytoplasm, is studied.... 相似文献
6.
High‐Energy Long‐Lived Mixed Frenkel–Charge‐Transfer Excitons: From Double Stranded (AT)n to Natural DNA 下载免费PDF全文
Dr. Ignacio Vayá Dr. Johanna Brazard Dr. Miquel Huix‐Rotllant Dr. Arun K. Thazhathveetil Prof. Frederick D. Lewis Dr. Thomas Gustavsson Prof. Dr. Irene Burghardt Dr. Roberto Improta Dr. Dimitra Markovitsi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4904-4914
The electronic excited states populated upon absorption of UV photons by DNA are extensively studied in relation to the UV‐induced damage to the genetic code. Here, we report a new unexpected relaxation pathway in adenine–thymine double‐stranded structures (AT)n. Fluorescence measurements on (AT)n hairpins (six and ten base pairs) and duplexes (20 and 2000 base pairs) reveal the existence of an emission band peaking at approximately 320 nm and decaying on the nanosecond time scale. Time‐dependent (TD)‐DFT calculations, performed for two base pairs and exploring various relaxation pathways, allow the assignment of this emission band to excited states resulting from mixing between Frenkel excitons and adenine‐to‐thymine charge‐transfer states. Emission from such high‐energy long‐lived mixed (HELM) states is in agreement with their fluorescence anisotropy (0.03), which is lower than that expected for π–π* states (≥0.1). An increase in the size of the system quenches π–π* fluorescence while enhancing HELM fluorescence. The latter process varies linearly with the hypochromism of the absorption spectra, both depending on the coupling between π–π* and charge‐transfer states. Subsequently, we identify the common features between the HELM states of (AT)n structures with those reported previously for alternating (GC)n: high emission energy, low fluorescence anisotropy, nanosecond lifetimes, and sensitivity to conformational disorder. These features are also detected for calf thymus DNA in which HELM states could evolve toward reactive π–π* states, giving rise to delayed fluorescence. 相似文献
7.
Irene Gouvinhas Nelson Machado Amadeo Girons‐Vilaplana Snia Gomes Teresa Carvalho Raúl Domínguez‐Perles Ana I. R. N. A. Barros 《Journal of Chemometrics》2016,30(9):548-558
The olive tree (Olea europaea L.) can be affected by Colletotrichum acutatum, causing a loss of yield and quality of the final products, whilst the incidence of this fungal infection depends on several factors, including cultivar susceptibility. Thus, the effect of C. acutatum infection in cultivars displaying different susceptibilities to this fungal disease (‘Galega Vulgar’ ‐ susceptible, ‘Cobrançosa’ ‐ moderately susceptible, ‘Picual’ ‐ tolerant) has been assessed through spectrophotometric methods and HPLC, while the FTIR spectra of the cuticles have been concomitantly registered, resorting to the ATR accessory. With the support of multivariate analysis, these spectra allowed to discriminate olives with distinct infection times, besides retrieving evidences concerning the different susceptibility of each cultivar, while these observations were reinforced by the spectrophotometric and chromatographic methods. Furthermore, the assessment of the phenolic profile evidenced individual compounds in the distinct cultivars, so as their variations in response to the fungal infection. 相似文献
8.
Franciani C. Sentanin Willian R. Caliman Rodrigo C. Sabadini Carla C. S. Cavalheiro Rui F. P. Pereira Maria M. Silva Agnieszka Pawlicka 《Molecules (Basel, Switzerland)》2021,26(8)
Nanocomposite polymer electrolytes (NPEs) were synthesized using sodium alginate (Alg) and either sodium (SCa-3-Na+)- or lithium (SCa-3-Li+)-modified montmorillonite clays. The samples were characterized by structural, optical, and electrical properties. SCa-3-Na+ and SCa-3-Li+ clays’ X-ray structural analyses revealed peaks at 2θ = 7.2° and 6.7° that corresponded to the interlamellar distances of 12.3 and 12.8 Å, respectively. Alg-based NPEs X-ray diffractograms showed exfoliated structures for samples with low clay percentages. The increase of clay content promoted the formation of intercalated structures. Electrochemical Impedance Spectroscopy revealed that Alg-based NPEs with 5 wt% of SCa-3-Na+ clay presented the highest conductivity of 1.96 × 10−2 S/cm2, and Alg with 10 wt% of SCa-3-Li+ showed conductivity of 1.30 × 10−2 S/cm2, both measured at 70 °C. From UV-Vis spectroscopy, it was possible to infer that increasing concentration of clay promoted a decrease of the samples’ transmittance and, consequently, an increase of their reflectance. 相似文献
9.
Dr. Elisa Bonandi Dr. Mattia Mori Dr. Paola Infante Dr. Irene Basili Prof. Dr. Lucia Di Marcotullio Dr. Andrea Calcaterra Dr. Federica Catti Prof. Dr. Bruno Botta Prof. Dr. Daniele Passarella 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(32):8350-8357
Withanolides constitute a well-known family of plant-based alkaloids characterised by widespread biological properties, including the ability of interfering with Hedgehog (Hh) signalling pathway. Following our interest in natural products and in anticancer compounds, we report here the synthesis of a new class of Hh signalling pathway inhibitors, inspired by withaferin A, the first isolated member of withanolides. The decoration of our scaffolds was rationally supported by in silico studies, while functional evaluation revealed promising candidates, confirming once again the importance of natural products as inspiration source for the discovery of novel bioactive compounds. A stereoselective approach, based on Brown chemistry, allowed the obtainment and the functional evaluation of the enantiopure hit compounds. 相似文献
10.
Supercritical fluid extraction (SFE) is a green alternative method of extraction for neutral lipids in seeds compared to conventional methods utilizing organic solvents. In this work, a novel method where SFE is hyphenated with an evaporative light scattering detector is presented. The method was subsequently applied to determine lipid content in crushed linseed. The new method enables rapid quantification of extracted lipids as well as be ability to continuously monitor the extraction rate in real-time, thus being able to determine the time point of completed extraction. 相似文献