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21.
Dr. Andre Nicolai Petelski Josefina Marquez Silvana Carina Pamies Prof. Dr. Gladis Laura Sosa Prof. Dr. Nélida María Peruchena 《Chemphyschem》2021,22(7):665-674
Due to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C−H bond is as effective as the N−H bond to coordinate chloride. An analysis of the electron charge density at the C−H⋅⋅⋅Cl− and N−H⋅⋅⋅Cl− bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C−H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C−H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl. 相似文献
22.
Tiziana Forleo Alessandro Zappi Dora Melucci Martina Ciriaci Francesco Griffoni Simone Bacchiocchi Melania Siracusa Tamara Tavoloni Arianna Piersanti 《Molecules (Basel, Switzerland)》2021,26(9)
The international seafood trade is based on food safety, quality, sustainability, and traceability. Mussels are bio-accumulative sessile organisms that need regular control to guarantee their safe consumption. However, no well-established and validated methods exist to trace mussel origin, even if several attempts have been made over the years. Recently, an inorganic multi-elemental fingerprint coupled to multivariate statistics has increasingly been applied in food quality control. The mussel shell can be an excellent reservoir of foreign inorganic chemical species, allowing recording long-term environmental changes. The present work investigates the multi-elemental composition of mussel shells, including Al, Cu, Cr, Zn, Mn, Cd, Co, U, Ba, Ni, Pb, Mg, Sr, and Ca, determined by inductively-coupled plasma mass-spectrometry in Mytilus galloprovincialis collected along the Central Adriatic Coast (Marche Region, Italy) at 25 different sampling sites (18 farms and 7 natural banks) located in seven areas. The experimental data, coupled with chemometric approaches (principal components analysis and linear discriminant analysis), were used to create a statistical model able to discriminate samples as a function of their production site. The LDA model is suitable for achieving a correct assignment of >90% of individuals sampled to their respective harvesting locations and for being applied to counteract fraud. 相似文献
23.
The static dielectric properties of (001)(GaAs)(p)/(AlAs)(p) superlattices have been calculated as a function of their period p for 1< or = p < or =12, starting from density-functional theory. The interplay between quantum confinement and local field effects is shown to be crucial. For light polarized in the growth direction it leads to the otherwise surprising justification of the use of a classical effective medium theory, even for the smallest periods. Only the inclusion of both contributions allows in ab initio and in semiempirical calculations to reproduce the experimentally observed birefringence. 相似文献
24.
Baldini M Belicchi-Ferrari M Bisceglie F Pelosi G Pinelli S Tarasconi P 《Inorganic chemistry》2003,42(6):2049-2055
Two new 5-formyluracil thiosemicarbazone (H(3)ut) derivatives, Me-H(3)ut (1) and Me(2)-H(3)ut (2), were synthesized by reacting thiosemicarbazides, mono- and dimethylated on the aminic nitrogen, with 5-formyluracil and were subsequently characterized. These ligands, treated with copper chloride and nitrate, afforded three complexes: [Cu(Me-H(3)ut)Cl(2)].H(2)O (3), [Cu(Me(2)-H(3)ut)Cl(2)].H(2)O (4), and [Cu(Me-H(3)ut)(NO(3))(OH(2))(2)]NO(3) (5). The crystal structures of these complexes have been determined by single-crystal X-ray diffraction. In 3 and 4, a similar pentacoordination is present; the copper atom is surrounded by the ligand SNO donor atoms and by two chloride ions. The structure of 5 consists of [Cu(Me-H(3)ut)(NO(3))(OH(2))(2)](+) cations and nitrate anions. The copper coordination (4 + 2) involves the SNO ligand atoms and a water oxygen in the basal plane; the apical positions are occupied by a second water oxygen and by an oxygen of a monodentate nitrate group. Two biochemical techniques, namely DNA titration in the UV-vis region and thermal denaturation, have been employed to probe the details of DNA binding of these compounds. Analysis of the results suggests that our compounds are able to interact with DNA by electrostatic and groove binding but not by intercalation. The compounds have been also tested in vitro on human leukemic cell line U937, but they are not able to inhibit significantly cell proliferation. 相似文献
25.
The structure of groups in which many subgroups have a certain property X has been investigated for several choices of the property X. Groups whose non-normal subgroups satisfy certain finite rank conditions are studied in this article. In particular, a classification of groups in which every subgroup is either normal or polycyclic is given.(Dedicated to Mario Curzio on the occasion of his 70th birthday)1991 Mathematics Subject Classification: 20F16 相似文献
26.
Montserrat Cortina‐Puig Anastasia C. H. Scangas Zachary S. Marchese Silvana Andreescu Jean‐Louis Marty Carole Calas‐Blanchard 《Electroanalysis》2010,22(20):2429-2433
This paper describes the development of a xanthine oxidase/poly‐m‐phenylenediamine (XOD‐PPD)‐modified electrode. The biosensor was constructed by encapsulating XOD in a sol‐gel matrix deposited onto a platinum based screen‐printed electrode functionalized with a permselective PPD membrane. The hydrogen peroxide generated as a final product of the enzymatic reaction between the hypoxanthine and the XOD or by the spontaneous dismutation of superoxide radicals was selectively monitored at +700 mV. The use of a highly selective PPD layer blocked the nonspecific oxidation of other oxidizable molecules. Finally the biosensor was applied to the determination of the antioxidant capacity of acetylsalicylic acid. 相似文献
27.
Silvana L. Giudicessi M. Kaniz Fatema Hiroshi Nonami Rosa Erra-Balsells 《Journal of the American Society for Mass Spectrometry》2010,21(9):1526-1529
The effect of Ca2+ (and Mg2+) and the disodium salt of ethylenediaminetetraacetic acid (EDTA), a well known Ca2+ (and Mg2+) chelating agent, on the volatilization/ionization of carbohydrates by using electrospray ionization mass spectrometry has
been studied. Model compounds such as maltoses (maltose to maltoheptaose), β-cyclodextrins (β-cyclodextrin, methyl-β-cyclodextrin,
heptakis(2,6-di-O-methyl)-β-cyclodextrin, heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin, and 2-hydroxypropyl-β-cyclodextrin)
and fructans (sucrose, 1-ketose, nystose, and 1F-fructofuranosylnystose) were used. 相似文献
28.
Flores-Livas JA Debord R Botti S San Miguel A Marques MA Pailhès S 《Physical review letters》2011,106(8):087002
We present a joint experimental and theoretical study of the superconducting phase of the layered binary silicide BaSi(2). Compared with the AlB(2) structure of graphite or diboridelike superconductors, in the hexagonal structure of binary silicides the sp(3) arrangement of silicon atoms leads to corrugated sheets. Through a high-pressure synthesis procedure we are able to modify the buckling of these sheets, enhancing the superconducting transition temperature from 6 to 8.9 K when the silicon planes flatten out. By performing ab initio calculations based on density-functional theory we explain how the electronic and phonon properties are strongly affected by changes in the buckling. This mechanism is likely present in other intercalated layered superconductors, opening the way to the tuning of superconductivity through the control of internal structural parameters. 相似文献
29.
Cecilia E. Silvana Alvaro Alicia D. Ayala Norma S. Nudelman 《Journal of Physical Organic Chemistry》2011,24(2):101-109
The kinetics of the reactions of 2,4‐dinitrofluorobenzene (DNFB) and 2,4‐dinitrochlorobenzene (DNClB) with 2‐guanidinobenzimidazole (2‐GB) at 40 ± 0.2 °C in dimethylsulphoxide (DMSO), toluene, and in toluene–DMSO mixtures, and with 1‐(2‐aminoethyl)piperidine (2‐AEPip) and N‐(3‐aminopropyl)morpholine (3‐APMo) in toluene at 25 ± 0.2 °C were studied under pseudo first‐order conditions. For the reactions of 2‐GB carried out in pure DMSO, the second‐order rate coefficients were independent of the amine concentration. In contrast, the reactions of 2‐GB with DNFB in toluene, showed a kinetic behaviour consistent with a base‐catalysed decomposition of the zwitterionic intermediate. These results suggest an intramolecular H‐bonding of 2‐GB in toluene, which is not present in DMSO. To confirm this interpretation the reactions were studied in DMSO–toluene mixtures. Small amounts of DMSO produce significant increase in rate that is not expected on the basis of the classical effect of a dipolar aprotic medium; the effect is consistent with the formation of a nucleophile/co‐solvent mixed aggregate. For the reactions of 3‐APMo with both substrates in toluene, the second‐order rate coefficients, kA, show a linear dependence on the [amine]. 3‐APMo is able to form a six‐membered ring by an intramolecular H‐bond which prevents the formation of self‐aggregates. In contrast, a third order was observed in the reactions with 2‐AEPip: these results can be interpreted as a H‐bonded homo‐aggregate of the amine acting as a better nucleophile than the monomer. Most of these results can be well explained within the frame of the ‘dimer nucleophile’ mechanism. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
30.
Romualdo Caputo Annalisa Guaragna Giovanni Palumbo Silvana Pedatella Francesco Solla 《Journal of carbohydrate chemistry》2013,32(4-5):631-634
In a recent paper2 we have reported the design and synthesis of 3-C-lithiated 5,6-dihydro-1,4-dithiin-2-yl[(4-methoxybenzyl)oxy]methane (1) which can be utilized as an allylic alcohol anion equivalent and leads to three-carbon elongations of various electrophiles by introduction of a fully protected hydroxypropenyl moiety. The latter contains a double bond, which can be unravelled to the cis configuration by diastereoselective removal3 of the dimethylene-disulfur bridge, as well as a protected primary hydroxyl group that, depending on the deprotection conditions used (DDQ/NaBH4 or DDQ), may either lead to the free allylic alcohol or to an α,β-unsaturated aldehyde. 相似文献