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41.
42.
Bergamaschi G Boiocchi M Monzani E Amendola V 《Organic & biomolecular chemistry》2011,9(24):8276-8283
The influence of the positively charged N-methylpyridinium substituent on the anion binding tendencies of urea-based receptors has been investigated by comparing molecules 1 and 2. These receptors have been studied in acetonitrile, by performing UV-vis. and (1)H NMR titrations with several anions. UV-vis. titrations have also been performed in DMSO, MeOH and CHCl(3)/CH(3)CN mixture (1/1, v/v). In the case of 1, the presence of both H-donor and H-acceptor groups (urea and pyridine, respectively) favours aggregation and the formation of dimers in the solid state. In solution, this tendency to aggregate reduces affinity for anions with respect to the similar urea-based receptor 3. The methylation of the pyridyl group of 1 leads to the pyridinium-containing receptor 2. The pyridinium positive charge enhances the acidity of urea and increases anion affinity, as evidenced by the comparison of the binding constants. Both receptors (1-2) form stable adducts with all investigated anions. However, in the case of 2, the formation of 1?:?1 adducts with basic anions, such as acetate and fluoride, is followed by a proton transfer process. Quite interestingly, deprotonation does not involve the urea group, thus preserving the 1?:?1 adduct, as demonstrated by the (1)H NMR measurements. In particular, the proton transfer process takes place at the methylene group linking the pyridinium fragment to the receptor's skeleton. (1)H NMR studies indicate the formation of a stable neutral methine species, characterised by the loss of aromaticity by the pyridyl ring. These results open new perspectives in the field of anion recognition, as receptor 2 may by applied to the monitoring of both bound anion (through the urea unit) and excess anion in solution (through the development of the yellow methine species). 相似文献
43.
44.
Valeria Romanucci Armando Zarrelli Annalisa Guaragna Cinzia Di Marino Giovanni Di Fabio 《Tetrahedron letters》2017,58(12):1227-1229
New phosphorylating reagents 1 and 2 were prepared in three steps from 4-hydroxybenzaldehyde. They showed good efficiency in the solid phase synthesis of 5′-phosphate monoester nucleosides. End-phosphate DNA sequence synthesis demonstrated the efficiency of the new reagents (1 and 2) according to the general procedure of automated DNA synthesis. The oxidation of P(III) to P(V) and the removal of benzyl protecting groups were achieved in a single step by treatment with a 0.02 M I2/pyridine/H2O solution. Due to this one-pot treatment, it is possible to use the phosphorylating reagents (1 and 2) for the synthesis of base-sensitive ODNs. The reagents 1 and 2 are unique among phosphorylating reagents. 相似文献
45.
Olga N. Pestova Andrey Yu. Efimov Lyubov A. Myund Andrei G. Kudrev Vasiliy D. Khripun Anna G. Davidian Valeria E. Baranauskaite 《Journal of solution chemistry》2017,46(9-10):1854-1870
A new approach has been proposed to study the structure of aqueous electrolyte solutions. NIR, Raman and attenuated total reflectance, Fourier transform infra-red (ATR FTIR) spectra have been measured for aqueous calcium perchlorate solutions in the 0.22–4.3 mol·L?1 (0.22–7.46 mol·kg?1) concentration range at 25 °C. By the methods of principal component analysis (PCA) and multivariate curve resolution—alternating least squares (MCR-ALS) the number, spectra and concentration profiles have been determined for spectroscopically distinguishable forms of water and ClO 4 ? ion in solutions. The results have been analyzed using a phenomenological model, establishing thereby: concentration ranges for structural rearrangements of the solution, the nature of structural microirregularities and different states of the ClO 4 ? ion in the areas of domination of the natural water structure, and of cybotactic groups of calcium perchlorate hexa and tetra hydrates. 相似文献
46.
Roberta Sanna Davide Sanna Valeria Alzari Daniele Nuvoli Sergio Scognamillo Massimo Piccinini Massimo Lazzari Emilia Gioffredi Giulio Malucelli Alberto Mariani 《Journal of polymer science. Part A, Polymer chemistry》2012,50(19):4110-4118
Thermoresponsive poly(N‐vinylcaprolactam) nanocomposite hydrogels containing graphene were successfully prepared by frontal polymerization. High concentration of graphene (5.0 mg/mL) was obtained by direct graphite sonication in the self‐same liquid monomer, thus avoiding any chemical manipulation and obtaining “real” graphene as nanofiller instead of one of its more or less oxidized derivative, which is what generally reported in published reports. Furthermore, the corresponding nanocomposites were obtained without using any solvent to be eventually removed. The materials were fully characterized by RAMAN, SEM, and TEM, and their swelling behavior and rheological properties were investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
47.
Carmen FestaSimona De Marino Valentina SepeMaria Valeria D’Auria Giuseppe BifulcoRosa Andrés Maria Carmen TerencioMiguel Payá Cécile DebitusAngela Zampella 《Tetrahedron》2011,67(40):7780-7786
Two new cyclopeptides, perthamides E and F were isolated from the polar extracts of the sponge Theonella swinhoei. The new structures, featuring an unprecedented β-amino acid unit (AHMOA), were determined by interpretation of NMR and MS data. The absolute configuration of the AHMOA residue was proposed on the basis of quantum chemical calculation of NMR chemical shifts. Perthamides were proved to inhibit TNF-α and IL-8 release in primary human keratinocytes cells and therefore could represent potentially leads for the treatment of psoriasis. 相似文献
48.
49.
Ortiz W Krueger BP Kleiman VD Krause JL Roitberg AE 《The journal of physical chemistry. B》2005,109(23):11512-11519
We present a theoretical investigation of energy transfer in the phenylene ethynelene dendrimer known as the nanostar. Data from extensive molecular dynamics simulations are used to model the dynamical effects caused by torsional motion of the phenyl groups. We compare rate constants for energy transfer between the two-ring chromophore and the three-ring chromophore obtained via the F?rster model, the ideal dipole approximation (IDA), and the transition density cube (TDC) method, which has as its limit an exact representation of the Coulombic coupling. We find that the rate constants obtained with the TDC are extremely sensitive to the phenyl group rotation, whereas the constants computed with the F?rster model and the IDA are not. The implications of these results for the interpretation of recent pump-probe experiments on the nanostar are discussed in detail. Finally, we predict the temperature dependence of the rate constant for energy transfer. 相似文献
50.
We propose an alternative new material (2,4,5-trifluoroimidazole impregnated Nafion) for use as a high-temperature, water-free membrane for proton-exchange membrane fuel cells. This material has been tested computationally using molecular dynamics and quantum mechanics techniques, leading to an estimated conductivity of approximately 0.06 S/cm at 177 degrees C. This material overcomes the weakness of the imidazole-impregnated membranes, i.e., the poisoning of the Pt electrode. We find that 2,4,5-trifluoroimidazole binds weakly to platinum surfaces, so poisoning is not expected. 相似文献