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31.
Swart M Fonseca Guerra C Bickelhaupt FM 《Journal of the American Chemical Society》2004,126(51):16718-16719
Recently, Vakonakis and LiWang (J. Am. Chem. Soc. 2004, 126, 5688) reported experimental evidence for stronger hydrogen bonds in RNA A:U than in DNA A:T base pairs, which was based on differences in NMR shielding for adenine C2. We have analyzed the proposed correlation between NMR shielding and hydrogen-bond strength using density functional theory. Although we agree with the conclusion that A:U is more strongly bound, we find no correlation between the hydrogen-bond strength and the NMR shielding of C2. Our study shows that NMR merely probes the presence/absence of the methyl group in thymine/uracil, without any relation to the strength of the hydrogen bonds involved. In other words, one cannot infer the Watson-Crick hydrogen-bond strength from the NMR shielding constant of adenine C2. 相似文献
32.
Dr. Olatz Larrañaga Prof. Dr. Ana Arrieta Prof. Dr. Célia Fonseca Guerra Prof. Dr. F. Matthias Bickelhaupt Dr. Abel de Cózar 《化学:亚洲杂志》2021,16(4):315-321
We have quantum chemically studied the structure and nature of alkali- and coinage-metal bonds (M-bonds) versus that of hydrogen bonds between A−M and B− in archetypal [A−M⋅⋅⋅B]− model systems (A, B=F, Cl and M=H, Li, Na, Cu, Ag, Au), using relativistic density functional theory at ZORA-BP86-D3/TZ2P. We find that coinage-metal bonds are stronger than alkali-metal bonds which are stronger than the corresponding hydrogen bonds. Our main purpose is to understand how and why the structure, stability and nature of such bonds are affected if the monovalent central atom H of hydrogen bonds is replaced by an isoelectronic alkali- or coinage-metal atom. To this end, we have analyzed the bonds between A−M and B− using the activation strain model, quantitative Kohn-Sham molecular orbital (MO) theory, energy decomposition analysis (EDA), and Voronoi deformation density (VDD) analysis of the charge distribution. 相似文献
33.
Recently, some of us reviewed the synthes is and chemical reactions of conjugated azoalkenes.1 Emphasis was placed on the fact that these derivatives represent at the same time interesting products and useful intermediates in organic chemistry. In fact, conjugated azoolefins undergo a wide range of 1,4-additions, (3+2)- and (4+2)-cycloadditions allowing various functionalizations of the carbon atom adjacent to the carbonyl group, and the construction of many types of interesting five - and six-membered heterocycles, such as widely substituted pyrrole and pyridazine rings. These relevant synthetic objectives appear not to be smoothly obtained by other procedures. In addition, many of the compounds produced from conjugated azoalkenes can profitably be employed in the preparation of natural, pharmaceutical, and phytopharmaceutical products.1 相似文献
34.
Darwin P. R. Kint Antxon Martinez de Ilarduya Jordi J. Bou Sebastin Muoz‐Guerra 《Journal of polymer science. Part A, Polymer chemistry》2002,40(14):2276-2285
The methanolytic degradation of poly(ethylene terephthalate) (PET) copolymers containing nitroterephthalic units was investigated. Random poly(ethylene terephthalate‐co‐nitroterephthalate) copolyesters (PETNT) containing 15 and 30 mol % nitrated units were prepared from ethylene glycol and a mixture of dimethyl terephthalate and dimethyl nitroterephthalate. A detailed study of the influence of the nitro group on the methanolytic degradation rate of the nitrated bis(2‐hydroxyethyl) nitroterephthalate (BHENT) model compound in comparison with the nonnitrated bis(2‐hydroxyethyl) terephthalate (BHET) model compound was carried out. The kinetics of the methanolysis of BHENT and BHET were evaluated with high‐performance liquid chromatography and 1H NMR spectroscopy. BHENT appeared to be much more reactive than BHET. The methanolytic degradation of PET and PETNT copolyesters at 80 °C was followed by changes in the weight and viscosity, gel permeation chromatography, differential scanning calorimetry, scanning electron microscopy, and 1H and 13C NMR spectroscopy. The copolyesters degraded faster than PET, and the degradation increased with the content of nitrated units and occurred preferentially by cleavage of the ester groups placed at the meta position of the nitro group in the nitrated units. For both PET and PETNT copolyesters, an increase in crystallinity accompanied methanolysis. A surface degradation mechanism entailing solubilization of the fragmented polymer and consequent loss of mass was found to operate in the methanolysis of the copolyesters. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2276–2285, 2002 相似文献
35.
Paola Rizzo Vincenzo Venditto Gaetano Guerra Antonio Vecchione 《Macromolecular Symposia》2002,185(1):53-63
The different kinds of crystalline orientations which can occur in industrially relevant isotactic polypropylene (i-PP) films are compared with those generally observed for other semicrystalline polymers. The peculiar bimodality typical of the uniplanar-axial orientation which is present in two-step biaxially stretched i-PP films is rationalized in terms of the two alternative stackings on the (0k0) face of bilayers of macromolecules of the monoclinic unit cell. 相似文献
36.
Dr. Cristian Guerra Dr. Leandro Ayarde-Henríquez Dr. Yeray A. Rodríguez-Núñez Prof. Adolfo Ensuncho Prof. Dr. Eduardo Chamorro 《Chemphyschem》2023,24(11):e202200867
In this study, we revealed the significance of chemical bonding for the photochemically induced mechanism of 2-phenyl tetrazole derivatives generating nitrile imines. The correlated electron localization function shows that the formation of imine nitrile involves two key bond events: (i) the heterolytic C−N breakage taking place in the T1 state and (ii) the homolytic N−N rupture occurring in the T2 excited state. In particular, a cation-radical specie results from the C−N cleavage, whereas the N−N rupture creates a biradical resonant form of imine nitrile. Additionally, we noticed that the substantial pair delocalization of the C−C-N bonded structure could play a significant role in the conversion of the biradical imine nitrile into both the propargylic and allenic forms via the T1→S0 deactivation. 相似文献
37.
Summary The retention, selectivity and elution order of fluorescent 1,N6-etheno derivatives of diadenosine polyphosphates and their enzymatic degradation products on octadecyl and phenyl-bonded
silica columns have been studied as a function of mobile phase pH, ionic strength and organic modifier content. Good separations
of the compounds of interest were achieved using mobile phases of around 0.1M potassium phosphate buffers at neutral pH containing
approximately 10% methanol or 4% acetonitrile for C18 columns and 5% methanol or 1.5% acetonitrile for phenyl columns. The data obtained were used to establish isocratic assays
for diadenosine polyphosphate cleaving activities from chromaffin cells using Di(1,N6-ethenoadenosine) polyphosphates as fluorogenic substrate analogues followed by fluorescence detection. 相似文献
38.
Gaetano Guerra Odda Ruiz De Ballesteros Vincenzo Venditto Maurizio Galimberti Franco Sartori Rachele Pucciariello 《Journal of Polymer Science.Polymer Physics》1999,37(11):1095-1103
Structural (X‐ray diffraction), melting (differential scanning calorimetry), as well as mechanical (tensile tests) characterizations on uncrosslinked ethene–propene copolymer samples, obtained using a metallocene‐based catalytic system and having an ethene content in the range 80–50% by mol, are reported. Samples with an ethene content in the range 80–60% by mol present a disordered pseudohexagonal crystalline phase, whose melting moves from ≈ 40°C down to ≈ −20°C as the ethene content is reduced. The dramatic influence of the crystalline phase on tensile properties of uncrosslinked ethene–propene copolymers is shown. In particular, highest elongation at break values are obtained for samples being essentially amorphous in the unstretched state and partially crystallizing under stretching. On the other hand, lowest tension set values (most elastic behavior) are observed for samples presenting, already in the unstretched state, microcrystalline domains acting as physical crosslinks in a prevailing amorphous phase. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1095–1103, 1999 相似文献
39.
Giuseppe Milano Gaetano Guerra Luigi Cavallo 《Macromolecular theory and simulations》2001,10(4):349-354
40.
Misbahul Ain Khan Alina Guerra Cosenza Gwynn Pennant Ellis 《Journal of heterocyclic chemistry》1982,19(5):1077-1085
Various 1H,6H-pyrano[2,3-c]pyrazol-6-ones (III-XXIII) were obtained from β-keto esters and 1H-pyrazol-5-ones or hydrazines. Nitrations, chlorinations and brominations of these pyranopyrazoles were also carried out giving the corresponding derivatives (XXIV-LXIV). The pyrone ring is the more reactive one in these reactions and the preferred position of attack is the 5-position. The substitution products are formed by the addition-elimination route. 相似文献