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排序方式: 共有199条查询结果,搜索用时 15 毫秒
1.
Oláh J De Proft F Veszprémi T Geerlings P 《The journal of physical chemistry. A》2005,109(8):1608-1615
A detailed investigation of the electrophilic and nucleophilic character of singlet silylenes and germylenes, divalent compounds of silicon and germanium, respectively, substituted by first- and second-row elements is presented. In a first part, the Lewis acid properties of these compounds were studied through their complexation reaction with the Lewis bases NH3, PH3, and AsH3. The results indicate that this complexation is most favorable with the hardest base NH3, classifying these compounds as hard Lewis acids. This is confirmed by the linear correlation between the interaction energies and the value of the electrostatic potential, used as an approximation to the local hardness, near the empty p orbital of these compounds, indicating a charge-controlled interaction in the complex. Also the electrophilicity index, proposed by Parr et al., computed both at the global and the local level, correlates linearly with the complexation energies of the compounds with NH3. The Lewis base character of these silylenes has been investigated, through their interaction with the acids BH3 and AlH3. Also in this case, the electrostatic potential can be used to probe the reactivity of the compounds. It will finally be demonstrated that an increasing stability of the silylenes and germylenes is accompanied by an increase in their nucleophilicity and a decrease of the electrophilicity. 相似文献
2.
3.
Juan A. Allegretto Agustín Iborra Dr. Juan M. Giussi Dr. Catalina von Bilderling Dr. Marcelo Ceolín Dr. Sergio Moya Dr. Omar Azzaroni Dr. Matias Rafti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(54):12388-12396
This work reports on a novel and versatile approach to control the structure of metal–organic framework (MOFs) films by using polymeric brushes as 3D primers, suitable for triggering heterogeneous MOF nucleation. As a proof-of-concept, this work explores the use of poly(1-vinylimidazole) brushes primer obtained via surface-initiated atom transfer radical polymerization (SI-ATRP) for the synthesis of Zn-based ZIF-8 MOF films. By modifying the grafting density of the brushes, smooth porous films were obtained featuring inherently hydrophobic microporosity arising from ZIF-8 structure, and an additional constructional interparticle mesoporosity, which can be employed for differential adsorption of targeted adsorbates. It was found that the grafting density modulates the constructional porosity of the films obtained; higher grafting densities result in more compact structures, while lower grafting density generates increasingly inhomogeneous films with a higher proportion of interparticle constructional porosity. 相似文献
4.
In this paper we prove that weak solutions to the Diffusive Wave Approximation of the Shallow Water equations are locally bounded. Here, u describes the height of the water, z is a given function that represents the land elevation and f is a source term accounting for evaporation, infiltration or rainfall. 相似文献
5.
2D difference gel electrophoresis reference map of a Fusarium graminearum nivalenol producing strain
Matias Pasquali Tommaso Serchi Jenny Renaut Lucien Hoffmann Torsten Bohn 《Electrophoresis》2013,34(4):505-509
Fusarium graminearum is widely studied as a model for toxin production among plant pathogenic fungi. A 2D DIGE reference map for the nivalenol‐producing strain 453 was established. Based on a whole protein extract, all reproducible spots were systematically picked and analyzed by MALDI‐TOF/TOF, leading to the identification of 1102 protein species. The obtained map contributes to the annotation of the genome by identifying previously nondescribed hypothetical proteins and will serve as a reference for future studies aiming at deciphering F. graminearum biology and chemotype diversity. 相似文献
6.
Ahmed M. Rozza Marcell Papp Neil R. McFarlane Prof. Jeremy N. Harvey Dr. Julianna Oláh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202200930
The binding of small gas molecules such as NO and CO plays a major role in the signaling routes of the human body. The sole NO-receptor in humans is soluble guanylyl cyclase (sGC) – a histidine-ligated heme protein, which, upon NO binding, activates a downstream signaling cascade. Impairment of NO-signaling is linked, among others, to cardiovascular and inflammatory diseases. In the present work, we use a combination of theoretical tools such as MD simulations, high-level quantum chemical calculations and hybrid QM/MM methods to address various aspects of NO binding and to elucidate the most likely reaction paths and the potential intermediates of the reaction. As a model system, the H-NOX protein from Shewanella oneidensis (So H-NOX) homologous to the NO-binding domain of sGC is used. The signaling route is predicted to involve NO binding to form a six-coordinate intermediate heme-NO complex, followed by relatively facile His decoordination yielding a five-coordinate adduct with NO on the distal side with possible isomerization to the proximal side through binding of a second NO and release of the first one. MD simulations show that the His sidechain can quite easily rotate outward into solvent, with this motion being accompanied in our simulations by shifts in helix positions that are consistent with this decoordination leading to significant conformational change in the protein. 相似文献
7.
Lakovaara Matias Sirviö Juho Antti Ismail Mostafa Y. Liimatainen Henrikki Sliz Rafal 《Cellulose (London, England)》2021,28(9):5433-5447
Cellulose - In this work, deep eutectic solvent (DES) based on imidazole and triethylmethylammonium chloride was used as a reaction medium for the esterification of cellulose nanofiber (CNF) and... 相似文献
8.
Gonalo A. O. Tiago Inês A. S. Matias Ana P. C. Ribeiro Luísa M. D. R. S. Martins 《Molecules (Basel, Switzerland)》2020,25(24)
In this review, the roles of room temperature ionic liquids (RTILs) and RTIL based solvent systems as proposed alternatives for conventional organic electrolyte solutions are described. Ionic liquids are introduced as well as the relevant properties for their use in electrochemistry (reduction of ohmic losses), such as diffusive molecular motion and ionic conductivity. We have restricted ourselves to provide a survey on the latest, most representative developments and progress made in the use of ionic liquids as electrolytes, in particular achieved by the cyclic voltammetry technique. Thus, the present review comprises literature from 2015 onward covering the different aspects of RTILs, from the knowledge of these media to the use of their properties for electrochemical processes. Out of the scope of this review are heat transfer applications, medical or biological applications, and multiphasic reactions. 相似文献
9.
Inês A. S. Matias Ana P. C. Ribeiro Luísa M. D. R. S. Martins 《Molecules (Basel, Switzerland)》2020,25(23)
The direct, one-pot oxidation of ethane to acetic acid was, for the first time, performed using a C-scorpionate complex anchored onto a magnetic core-shell support, the Fe3O4/TiO2/[FeCl2{κ3-HC(pz)3}] composite. This catalytic system, where the magnetic catalyst is easily recovered and reused, is highly selective to the acetic acid synthesis. The performed green metrics calculations highlight the “greeness” of the new ethane oxidation procedure. 相似文献
10.
Carlos?M.?Matias Jo?o?M.?Sousa M.?Emília?Quinta-Ferreira Mona?Arif Hugh?D.?Burrows 《Journal of fluorescence》2010,20(1):377-380
Fura-2 is widely used as a fluorescent probe to monitor dynamic changes in cytosolic free calcium in cells, where Ca2+ can enter through several types of voltage-operated or ligand-gated channels. However, Fura-2 is also sensitive to other
metal ions, such as zinc, which may be involved in ionic channels and receptors. There is interest, in particular, in studying
the synapses between mossy fibers and CA3 pyramidal cells which contain both calcium and high quantities of free or loosely
bound zinc. We have found, through fluorescence probing, that endogenous zinc inhibits mossy fiber calcium transients. However,
since these results might be explained by an effect of the zinc chelator N,N,N’,N’-tetrakis(2-pyridylmethyl)ethylenediamine
(TPEN) on the spectral properties of Fura-2, we have carried out a validation of the method through fluorescence excitation
spectra of the complex Fura-2/calcium, and show that TPEN does not affect these spectra. This supports the idea that the observed
calcium enhancement is related to a zinc inhibition of presynaptic calcium mechanisms, and confirms the use of the chelator
TPEN as a general procedure for the biophysical study of Ca(II) in the presence of Zn(II) using Fura-2. 相似文献