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1.
Ander Camiruaga Dr. Imanol Usabiaga Dr. Camilla Calabrese Iker Lamas Prof. Francisco J. Basterretxea Dr. José A. Fernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(1):e202103636
One of the most fascinating questions in chemistry is why nature chose CGAT as the alphabet of life. Very likely, such selection was the result of multiple factors and a long period of refinement. Here, we explore how the intermolecular interactions influenced such process, by characterizing the formation of dimers between adenine, theobromine and 4-aminopyrimidine. Using a combination of mass-resolved excitation spectroscopy and DFT calculations, we determined the structure of adenine-theobromine and 4-aminopyrimidine-theobromine dimers. The binding energy of these dimers is very close to the canonical adenine-thymine nucleobases. Likewise, the dimers are able to adopt Watson-Crick conformations. These findings seem to indicate that there were many options available to build the first versions of the informational polymers, which also had to compete with other molecules, such as 4-aminopyrimidine, which does not have a valid attaching point for a saccharide. For some reason, nature did not select the most strongly-bonded partners or if it did, such proto-bases were later replaced by the nowadays canonical CGAT. 相似文献
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Christophe Raynaud Iker del Rosal Franck Jolibois Laurent Maron Romuald Poteau 《Theoretical chemistry accounts》2010,126(3-4):151-163
A new multicentered effective group potential (EGP) is obtained for η6-benzene. Applications on $[\hbox{Ru}_{4}(\hbox{H})_{4}(\hbox{C}_{6}\hbox{H}_{6})_{4}]^{n+}$ clusters (n = 0 or 2) are in excellent agreement with reference DFT studies in terms of geometries, energies and electronic structures. In particular, the small singlet–triplet energy difference (3.8 kcal mol?1) in [Ru4(H)4(C6H6)4]2+ is very well reproduced. This new EGP is nevertheless not free from the limitations associated to this first generation of molecular pseudopotentials. A cautious analysis of the nature and exact role of this EGP is made, which provides new directions for the elaboration of the next generation of EGPs. In addition, the η5-cyclopentadienyl EGP has been used to perform a constrained dynamical simulation for the reaction of Cp2LaH with H2. The energy conservation during the simulation as well as the activation barrier extracted from the simulation clearly demonstrate the good behavior of this EGP in the context of molecular dynamics. Anharmonic effects on this reaction are underlined, further demonstrating the high accuracy of the potential energy surface obtained with EGPs. From a more general point of view, such EGPs are expected to provide accurate albeit low-cost ligand-field effects in organometallic clusters or nanoparticles and to allow dynamical studies at the surface of such compounds. 相似文献
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Antolín R Borge G Posada T Raposo JC Seara I Etxebarria N 《Journal of AOAC International》2004,87(5):1218-1223
A validation study was carried out in order to evaluate the efficiency of inductively coupled plasma-optical emission spectrometry (ICP-OES) for the analysis of minor elements (manganese, chromium, copper, iron, and titanium) in aluminium alloys. Aluminium casting samples were obtained by adding compressed powder compacts of each alloying element and aluminium (minitablets) to aluminum baths in a laboratory crucible furnace. Digestion of solid samples was performed using concentrated HCI and H202 35% (v/v) previous to analysis by ICP-OES without any matrix separation. This solution-based method was validated considering direct current arc spectrometry as the reference method based on direct analysis without any pretreatment of the solid samples considered. Univariate statistical procedures were carried out, for which precision <3% and trueness of the analytical results were taken into account. 相似文献
4.
Dr. Viktor Pfeifer Marie Certiat Dr. Donia Bouzouita Dr. Alberto Palazzolo Sébastien Garcia-Argote Elodie Marcon David-Alexandre Buisson Dr. Philippe Lesot Prof. Laurent Maron Dr. Bruno Chaudret Dr. Simon Tricard Dr. Iker del Rosal Prof. Romuald Poteau Dr. Sophie Feuillastre Dr. Grégory Pieters 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):4988-4996
Ruthenium nanocatalysis can provide effective deuteration and tritiation of oxazole, imidazole, triazole and carbazole substructures in complex molecules using D2 or T2 gas as isotopic sources. Depending on the substructure considered, this approach does not only represent a significant step forward in practice, with notably higher isotope uptakes, a broader substrate scope and a higher solvent applicability compared to existing procedures, but also the unique way to label important heterocycles using hydrogen isotope exchange. In terms of applications, the high incorporation of deuterium atoms, allows the synthesis of internal standards for LC-MS quantification. Moreover, the efficacy of the catalyst permits, even under subatmospheric pressure of T2 gas, the preparation of complex radiolabeled drugs owning high molar activities. From a fundamental point of view, a detailed DFT-based mechanistic study identifying undisclosed key intermediates, allowed a deeper understanding of C−H (and N−H) activation processes occurring at the surface of metallic nanoclusters. 相似文献
5.
Iker AGIRREZABAL-TELLERIA Cristina GARCíA-SANCHO Pedro MAIRELES-TORRES Pedro Luis ARIAS 《催化学报》2013,34(7):1402-1406
The activity of Lewis (Nb2O5) and Br nsted (Amberlyst 70) acid catalysts for the cyclodehydration of xylose to furfural was studied. The nature of the acidity resulted in significant changes in the reaction mechanism. Lewis acid sites promote the formation of xylulose, while Br nsted acid sites are required to further dehydrate the sugar to furfural. Amberlyst 70 in water/toluene at 175 ℃ showed lower activity but gave a higher furfural yield. Using N2 as the stripping agent considerably improved the furfural yield and product purity in the stripped stream. Catalyst stability was also studied. 相似文献
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Del Rosal I Poteau R Maron L 《Dalton transactions (Cambridge, England : 2003)》2011,40(42):11228-11240
The influence of the initiator ligand on the Ring Opening Polymerization (ROP) of ε-caprolactone by lanthanide complexes grafted on silica have been investigated by means of density functional theory (DFT) calculations. Three different initiator ligands (alkyl, dialkylamido and borohydride) and three grating modes (mono-grafted, bi-grafted or bi-grafted after breaking of a Si-O-Si bridge) have been considered. This study highlights that lanthanum grafted complexes (alkyl, amide or borohydride) are active in lactone polymerization. In any case the reaction process is demonstrated to be similar to the one found for homogeneous catalysts. However, even if the different grafting modes are energetically equivalent for the ε-caprolactone ROP initiation reaction, some differences are observed according to the ligand involved in the initiation reaction. In agreement with experimental data, grafted lanthanide amides rapidly polymerise the ε-caprolactone. The grafted alkyl lanthanum complexes are also predicted to be very efficient catalysts. The borohydride is thus predicted to be the least efficient due to the difficulties in the ring opening. Indeed, the rate-determining step is the nucleophilic attack for the methyl and dialkylamido ligands (occuring with a low barrier) whereas it is the ring opening for the borohydride ligands (highest barrier) and the formation of -CH(2)C(=O)(X) (X = CH(3) or NMe(2)) terminal group is more favorable than that of a -CH(2)OBH(2) end group. 相似文献
9.
Dr. Quentin Le Dé Dr. Amal Bouammali Dr. Christian Bijani Dr. Laure Vendier Dr. Iker del Rosal Dr. Dmitry A. Valyaev Dr. Chiara Dinoi Dr. Antoine Simonneau 《Angewandte Chemie (International ed. in English)》2023,62(40):e202305235
We have re-examined the reactivity of the manganese dinitrogen complex [Cp(CO)2Mn(N2)] ( 1 , Cp=η5-cyclopentadienyl, C5H5) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N2)MnCOPh]Li ( 3 ) that is stable only below −40 °C. Full characterization of 3 (including single crystal X-ray diffraction) was performed. This complex decomposes quickly above −20 °C with N2 loss to give a phenylate complex [Cp(CO)2MnPh]Li ( 2 ). The latter compound was erroneously formulated as an anionic diazenido compound [Cp(CO)2MnN(Ph)=N]Li in earlier reports, ruling out the claimed and so-far unique behavior of the N2 ligand in 1 . DFT calculations were run to explore both the hypothesized and the experimentally verified reactivity of 1 with PhLi and are fully consistent with our results. Direct attack of a nucleophile on metal-coordinated N2 remains to be demonstrated. 相似文献
10.
Sneha Mullassery K. Yuvaraj Deepak Dange Dafydd D. L. Jones Iker del Rosal Ross O. Piltz Alison J. Edwards Laurent Maron Cameron Jones 《Angewandte Chemie (International ed. in English)》2023,62(30):e202305582
Reduction of a range of amido- and aryloxy-aluminum dihydride complexes, e.g. [AlH2(NR3){N(SiMe3)2}] (NR3=NMe3 or N-methylpiperidine (NMP)), with β-diketiminato dimagnesium(I) reagents, [{(ArNacnac)Mg}2] (ArNacnac=[HC(MeCNAr)2]−, Ar=mesityl (Mes) or 2,6-xylyl (Xyl)), have afforded deep red mixed valence aluminum hydride cluster compounds, [Al6H8(NR3)2{Mg(ArNacnac)}4], which have an average Al oxidation state of +0.66, the lowest for any well-defined aluminum hydride compound. In the solid-state, the clusters are shown to have distorted octahedral Al6 cores, having zero-valent Al axial sites and mono-valent AlH2− equatorial units. Several novel by-products were isolated from the reactions that gave the clusters, including the Mg−Al bonded magnesio-aluminate complexes, [(ArNacnac)(Me3N)Mg−Al(μ-H)3[{Mg(ArNacnac)}2(μ-H)]]. Computational analyses of one aluminum hydride cluster revealed its Al6 core to be electronically delocalized, and to possess one unoccupied, and six occupied, skeletal molecular orbitals. 相似文献