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101.
Effect of the π Bridge and Acceptor on Intramolecular Charge Transfer in Push–Pull Cationic Chromophores: An Ultrafast Spectroscopic and TD‐DFT Computational Study 下载免费PDF全文
Dr. Benedetta Carlotti Dr. Enrico Benassi Prof. Vincenzo Barone Dr. Giuseppe Consiglio Prof. Fausto Elisei Dr. Alessandra Mazzoli Prof. Anna Spalletti 《Chemphyschem》2015,16(7):1440-1450
Three (donor–π–acceptor)+ systems with a methyl pyridinium or quinolinium as the electron‐deficient group, a dimethyl amino as the electron‐donor group, and an ethylene or butadiene group as the spacer have been investigated in a joint spectroscopic and TD‐DFT computational study. A negative solvatochromism has been revealed in the absorption spectra, which implies a solution color change, and interpreted by considering the variation in the permanent dipole moment modulus and orientation upon photoexcitation. The fluorescence efficiency decreases upon increasing solvent polarity, in agreement with the excited‐state optimized geometries (planar in low‐polarity media and twisted in high‐polarity media). Femtosecond transient absorption has revealed the occurrence of a fast photoinduced intramolecular charge transfer (ICT) and the molecular factors that determine an efficient ICT. Considering the crucial role of the ICT in tuning the nonlinear optical (NLO) properties, these compounds can be considered promising NLO materials. 相似文献
102.
103.
Nicolis S Zucchelli M Monzani E Casella L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(28):8661-8673
The generation of reactive quinone species (DAQ) from oxidation of dopamine (DA) is involved in neurodegenerative pathologies like Parkinson's disease (A. Borta, G. U. H?glinger, J. Neurochem. 2007, 100, 587-595). The oxidation of DA to DAQ can occur either in a single two-electron process or in two consecutive one-electron steps, through semiquinone radicals, giving rise to different patterns of reactions. The former type of reaction can be promoted by tyrosinase, the latter by peroxidases in the presence of H(2)O(2), which can be formed under oxidative stress conditions. Both enzymes were employed for the characterization of the thiol-catechol adducts formed by reaction of DA and cysteine or glutathione, and for the identification of specific amino acid residues modified by DAQs in two representative target proteins, human and horse heart myoglobin. Our results indicate that the cysteinyl-DA adducts are formed from the same quinone intermediate independently of the mechanism of DA oxidation, and that the hallmark of a radical mechanism is the formation of the cystine dimer. The reactivity of quinone species also controls the DA-promoted derivatization of histidine residues in proteins. However, for the modification of the cysteine residue in human myoglobin, a radical intramolecular mechanism has been proposed, in which the protein acts both as the catalyst and target of the reaction. Most importantly, the modification of myoglobins through DAQ linkages, and in particular by DA oligomers, has dramatic effects on their stability, as it induces protein unfolding and incorporation into insoluble melanic precipitates. 相似文献
104.
Enrico Luchinat Letizia Barbieri Matteo Cremonini Alessio Nocentini Claudiu T. Supuran Lucia Banci 《Angewandte Chemie (International ed. in English)》2020,59(16):6535-6539
Structure‐based drug development is often hampered by the lack of in vivo activity of promising compounds screened in vitro, due to low membrane permeability or poor intracellular binding selectivity. Herein, we show that ligand screening can be performed in living human cells by “intracellular protein‐observed” NMR spectroscopy, without requiring enzymatic activity measurements or other cellular assays. Quantitative binding information is obtained by fast, inexpensive 1H NMR experiments, providing intracellular dose‐ and time‐dependent ligand binding curves, from which kinetic and thermodynamic parameters linked to cell permeability and binding affinity and selectivity are obtained. The approach was applied to carbonic anhydrase and, in principle, can be extended to any NMR‐observable intracellular target. The results obtained are directly related to the potency of candidate drugs, that is, the required dose. The application of this approach at an early stage of the drug design pipeline could greatly increase the low success rate of modern drug development. 相似文献
105.
106.
Gugliuzza A Aceto MC Macedonio F Drioli E 《The journal of physical chemistry. B》2008,112(34):10483-10496
Next generation PEEK-WC membranes have been fabricated by using an innovative self-assembly technique. Patterned architectures have been achieved via a solvent-reduced and water-assisted process, resulting in honeycomb packed geometry. The membranes exhibit monodisperse pores with size and shape comparable to those left by templating water droplets. Influencing factors for the formation of self-assembled poly-(etheretherketone) with Cardo [PEEK-WC] membranes have been evaluated, identifying the critical parameters for nucleation, growth, and propagation of the droplet-mobile arrays through the overall films. Structure-transport relationships have been discussed according to the results achieved from the implementation of membrane distillation processes, yielding indication about the suitability of self-assembled PEEK-WC films to work as interfaces in contactor operations. 相似文献
107.
Enrico Falcone Ikhlas M. M. Ahmed Dr. Valentina Oliveri Dr. Francesco Bellia Dr. Bertrand Vileno Dr. Youssef El Khoury Prof. Petra Hellwig Prof. Peter Faller Prof. Graziella Vecchio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(8):1871-1879
Mounting evidence supports the role of amyloidogenesis, oxidative stress, and metal dyshomeostasis in the development of neurodegenerative disorders. Parkinson's Disease is characterized by α-synuclein (αSyn) accumulation and aggregation in brain regions, also promoted by Cu2+. αSyn is modified by reactive carbonyl species, including acrolein (ACR). Notwithstanding these findings, the interplay between ACR, copper, and αSyn has never been investigated. Therefore, we explored more thoroughly the effects of ACR on αSyn using an approach based on LC-MS/MS analysis. We also evaluated the influence of Cu2+ on the protein carbonylation and how the ACR modification impacts the Cu2+ binding and the production of Reactive Oxygen Species (ROS). Finally, we investigated the effects of ACR and Cu2+ ions on the αSyn aggregation by dynamic light scattering and fluorescence assays. Cu2+ regioselectively inhibits the modification of His50 by ACR, the carbonylation lowers the affinity of His50 for Cu2+ and ACR inhibits αSyn aggregation both in the presence and in the absence of Cu2+. 相似文献
108.
Raffaele P. Bonomo Vincenzo Cucinotta Franca D' Allessandro Giuseppe Impellizzeri Giuseppe Maccarrone Enrico Rizzarelli Graziella Vecchio 《Journal of inclusion phenomena and macrocyclic chemistry》1993,15(2):167-180
The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]--cyclodextrin was synthesized, and an NMR, EPR, pH-metric, and calorimetric investigation was carried out in aqueous solution in order to ascertain its behaviour towards protonation and copper(II) complex formation. The thermodynamic parameters of the ternary complex formation with alanine, phenylalanine and tryptophan enantiomeric pairs were also determined (25° C andI=0.1 mol dm–3). No thermodynamic enantioselectivity was observed in these systems, while a chiral, though poor, discrimination was observed in LEC: c.d. spectra also show enantiomeric stereoselectivity. The results of the present investigation, compared with previously reported results, suggest the occurence of acis-complex trans-complex equilibrium in such systems. 相似文献
109.
Daniele Cauzzi Roberto Giordano Enrico Sappa Antonio Tiripicchio Marisa Tiripicchio Camellini 《Journal of Cluster Science》1993,4(3):279-296
The title complex (complex1) was the first alkyne-substituted triruthenium dihydrido cluster to be reported and was characterized by spectroscopy as a triangular cluster with the alkyne parallel to a Ru-Ru edge. Recently, we have found that1 is a key intermediate in the homogeneous hydrogenation of diphenylacetylene catalyzed by tetrahedral Ru4 and FeRu3 clusters. Since the discovery of1, a great number of complexes with alkynes parallel to a cluster edge have been reported; at present this is the more common bonding mode for alkynes on trinuclear clusters. The structural features of1 allow a comparison with those of other ruthenium-containing derivatives and help to draw suggestions of the role of1 in hydrogenation catalysis. 相似文献
110.
Giuseppe Bartoli Sandra Giuli Enrico Marcantoni Massimo Massaccesi 《Tetrahedron letters》2006,47(37):6501-6504
The arylidene malonates with two different geminal carboxylate functions, a suitable class of substrates of several synthetic and pharmacological studies, are easily available through Knoevenagel condensation of ethyl tert-butyl malonate and different aromatic aldehydes. The results have increased the potentialities of CeCl3·7H2O-NaI system as a type of water-tolerant green Lewis acid promoter for carbon-carbon bond forming procedures. 相似文献