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1.
Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes 下载免费PDF全文
Olena Mykhailiv Monika Imierska Martyna Petelczyc Prof. Dr. Luis Echegoyen Dr. Marta E. Plonska‐Brzezinska 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5783-5793
The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g?1 for the CNOs/Ppy bilayer (electrochemical deposition). 相似文献
2.
Triesterase and Promiscuous Diesterase Activities of a Di‐CoII‐Containing Organophosphate Degrading Enzyme Reaction Mechanisms 下载免费PDF全文
Dr. Marta E. Alberto Gaspar Pinto Prof. Nino Russo Dr. Marirosa Toscano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3736-3745
The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐CoII derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear CoII center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered. 相似文献
3.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
4.
Antonio R. Montoro Bustos Marta Garcia-Cortes Hector González-Iglesias Jorge Ruiz Encinar José M. Costa-Fernández Miguel Coca-Prados Alfredo Sanz-Medel 《Analytica chimica acta》2015
A generic strategy based on the use of CdSe/ZnS Quantum Dots (QDs) as elemental labels for protein quantification, using immunoassays with elemental mass spectrometry (ICP-MS), detection is presented. In this strategy, streptavidin modified QDs (QDs-SA) are bioconjugated to a biotinylated secondary antibody (b-Ab2). After a multi-technique characterization of the synthesized generic platform (QDs-SA-b-Ab2) it was applied to the sequential quantification of five proteins (transferrin, complement C3, apolipoprotein A1, transthyretin and apolipoprotein A4) at different concentration levels in human serum samples. It is shown how this generic strategy does only require the appropriate unlabeled primary antibody for each protein to be detected. Therefore, it introduces a way out to the need for the cumbersome and specific bioconjugation of the QDs to the corresponding specific recognition antibody for every target analyte (protein). Results obtained were validated with those obtained using UV–vis spectrophotometry and commercial ELISA Kits. 相似文献
5.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
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7.
András Gy. Németh Renáta Szabó Dr. Attila Domján Prof. György M. Keserű Dr. Péter Ábrányi-Balogh 《ChemistryOpen》2021,10(1):16-27
The development of a new three-component chromatography-free reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol. 相似文献
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9.
Periodica Mathematica Hungarica - In our paper we study the usage of partially defined Boolean functions (PDBFs) for generating cryptographically strong Boolean functions. A PDBF can be considered... 相似文献
10.
An analysis of the different philosophic and scientific visions of Henri Poincaré and Federigo Enriques relative to qualitative analysis provides us with a complex and interesting image of the “essential tension” between “tradition” and “innovation” within the history of science. In accordance with his scientific paradigm, Poincaré viewed qualitative analysis as a means for preserving the nucleus of the classical reductionist program, even though it meant “bending the rules” somewhat. To Enriques's mind, qualitative analysis represented the affirmation of a synthetic, geometrical vision that would supplant the analytical/quantitative conception characteristic of 19th-century mathematics and mathematical physics. Here, we examine the two different answers given at the turn of the century to the question of the relationship between geometry and analysis and between mathematics, on the one hand, and mechanics and physics, on the other.Copyright 1998 Academic Press.Un'analisi delle diverse posizioni filosofiche e scientifiche di Henri Poincaré e Federigo Enriques nei riguardi dell'analisi qualitativa fornisce un'immagine complessa e interessante della “tensione essenziale” tra “tradizione” e “innovazione” nell'ambito della storia della scienza. In linea con il proprio paradigma scientifico, Poincaré vedeva nell'analisi qualitativa un mezzo per preservare il nucleo del programma riduzionista calssico, anche se cio comportava una lieve “distorsione delle regole”. Nella mente di Enriques, l'analisi qualitativa rappresentava l'affermazione di un punto di vista sintetico e geometrico che avrebbe soppiantato la concezione analitico-quantitativa caratteristica della matematica e della fisica matematica del 19° secolo. Il nostro scopo principale è di esaminare due diverse risposte date a cavallo del secolo alla questione dei rapporti tra geometria e analisi e tra matematica da un lato e meccanica e fisica dall'altro.Copyright 1998 Academic Press.AMS subject classification: 01A55 相似文献