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21.
Product distribution, total quenching rate (kT), and rate of chemical reaction (kr) with singlet oxygen have been determined for some alkyl, benzyl, α-methylbenzyl, and cumyl sulfides. Their contributions depend on the steric hindering around the sulfur atom. In protic solvents, the sulfoxide is the main product via a hydrogen-bonded persulfoxide. In apolar solvents, intramolecular α-H abstraction leads to oxidative C-S bond cleavage, with varying efficiency. The behavior of sulfides is compared to that of alkenes and amines. 相似文献
22.
Sorption equilibrium of methanol on new composite sorbents “CaCl<Subscript>2</Subscript>/silica gel”
Yuri I. Aristov Larissa G. Gordeeva Yuri D. Pankratiev Ludmila M. Plyasova I. V. Bikova Angelo Freni Giovanni Restuccia 《Adsorption》2007,13(2):121-127
This paper presents experimental data on methanol sorption on new composite sorbents which consist of mesoporous silica gels
and calcium chloride confined to their pores. Sorption isobars and XRD analysis showed the formation of a solid crystalline
solvate CaCl2⋅2MeOH at low methanol uptake, while at higher uptake the formation of the CaCl2–methanol solution occurred. The solution confined to the silica pores showed the sorption properties similar to those of
the CaCl2–methanol bulk solution. Calorimetric and isosteric analyses showed that the heat of methanol sorption depends on the methanol
uptake, ranging from 38±2 kJ/mol for the solution to 81±4 kJ/mol for the solid crystalline phase CaCl2⋅2MeOH. The above mentioned characterizations allowed the evaluation of the methanol sorption and the energy storage capacities,
clearly showing that the optimal applications of these new composite sorbents are the methanol removal from gaseous mixtures,
heat storage and sorption cooling driven by low temperature heat. 相似文献
23.
Angelo J. Amoroso Brian F. G. Johnson Jack Lewis Chi-Keung Li Catherine A. Morewood Paul R. Raithby Maria D. Vargas Wing-Tak Wong 《Journal of Cluster Science》1995,6(1):163-173
Reduction of the heptaosmium cluster [Os7(CO)21] With [Et4N][NH4) gives the cluster dianion [Os7(CO)20]2–,1, in high yield. The reaction of the dianion with [AuPR
3Cl] (R=Et or Ph) in the presence of TlPF6 forms [Os7((CO)20(AuPR
3)2] [R=Et (2a);R = Ph(2b)] in 80% yield, while the corresponding reaction with (Os(C6H6)(CH3CN)3]2+ gives [Os8(CO)20 (
6-C6H6)] (3) in reasonable yield (ca. 30%). The dianion,1, and the clusters2 and3 have been fully characterized by bout spectroscopic and crystallographic methods. The crystal structure of the [Ph4P]+ salt of1 shows that the metals in the anion adopt a capped octahedral geometry, with all twenty carbonyl ligands in terminal sites. The metal core geometry in2a is best described as a tricapped octahedron, and is based on the structure of the dianion1 with two adjacent octahedral faces capped by the Au atoms of the two AuPEt3 groups. In a similar fashion, the geometry of3 is related to that of1 with the addition of an Os(C6H6) unit capped to a triangular face, to give a bicapped octahedral framework. 相似文献
24.
Gian Luigi Casalone Carla Mariani Angelo Mugnoli Massimo Simonetta 《Theoretical chemistry accounts》1967,8(3):228-235
On the basis of semiempirical calculations, the conformation of the isolated molecule of 2-bromo-1,1-diphenylprop-1-ene corresponding to the minimum of total energy was determined. Assuming some information on the localization of the molecules in the crystal, also the conformation in a theoretical crystal was studied. The results have been compared with the crystal structure of 2-bromo-1,1-diphenylprop-1-ene, as obtained by X-ray diffraction. From the comparison a slight displacement of the C2 atom was suggested.
This work was supported by a grant from the Italian Consiglio Nazionale delle Ricerche. 相似文献
Zusammenfassung Die dem Minimum der Gesamtenergie entsprechende Konformation des isolierten Moleküls von 2-Brom-1,1-diphenylprop-1-en wurde durch halb-empirische Methoden bestimmt. Gewisse Ergebnisse über die Anordnung der Moleküle im Kristall machten es möglich, die Konformation in einem theoretischen Kristall zu untersuchen. Nach Vergleich der Resultate mit der durch Röntgen-Analyse bestimmten Kristallstruktur des 2-Brom-1,1-diphenylprop-1-en wurde eine kleine Verschiebung des C2-Atoms vorgeschlagen.
Résumé Par le moyen de calculs semiempiriques on a déterminé la conformation de la molécule isolée de 2-bromo-1, 1-diphénilprop-1-ène, correspondant au minimum d'énergie totale. On a aussi étudié la conformation dans le cristal théorique en se basant sur des informations concernant la localisation des molécules dans le cristal. On a comparé ces résultats avec ceux que nous avons obtenus par la détermination de la structure cristalline du 2-bromo-1, 1-diphénilprop-1-ène avec la diffraction des rayons X: cette comparaison nous a porté à déplacer un petit peu l'atome C 2.
This work was supported by a grant from the Italian Consiglio Nazionale delle Ricerche. 相似文献
25.
The ab initio energies, nuclear and electron repulsions and charge distributions have been calculated using moderately large basis sets as a function of the RC N angle (R NH2, NF2 or PF2). The optimum RC N angles were calculated to be 178.9°, 176.6°, and 175° for NH2CN, NF2CN, and PF2CN, respectively. A rationalization of the differing bends is presented in terms of nuclear-nuclear and electron-electron repulsions. 相似文献
26.
Ti(III)-induced free-radical decomposition of a phenyldiazonium salt, followed by phenyl radical iodine-atom abstraction from alkyl iodides, leads to a one-pot selective alkyl radical addition to the C-atom of imines generated in situ under aqueous acidic conditions. [reaction: see text] 相似文献
27.
Valentina Gazzola Pietro Grisoli Valeria Amendola Giacomo Dacarro Carlo Mangano Piersandro Pallavicini Antonio Poggi Silvia Rossi Barbara Vigani Angelo Taglietti 《Molecules (Basel, Switzerland)》2022,27(17)
In this paper, we report on the preparation of Imidazole-functionalized glass surfaces, demonstrating the ability of a dinuclear Cu(II) complex of a macrocyclic ligand to give a “cascade” interaction with the deprotonated forms of grafted imidazole moieties. In this way, we realized a prototypal example of an antimicrobial surface based on a supramolecular approach, obtaining a neat microbicidal effect using low amounts of the described copper complex. 相似文献
28.
Claudio Tabolacci Deborah Giordano Stefania Rossi Martina Cordella Daniela DArcangelo Federica Moschella Stefania DAtri Mauro Biffoni Angelo Facchiano Francesco Facchiano 《Molecules (Basel, Switzerland)》2022,27(22)
Background: Despite recent improvements in therapy, the five-year survival rate for patients with advanced melanoma is poor, mainly due to the development of drug resistance. The aim of the present study was to investigate the mechanisms underlying this phenomenon, applying proteomics and structural approaches to models of melanoma cells. Methods: Sublines from two human (A375 and SK-MEL-28) cells with acquired vemurafenib resistance were established, and their proteomic profiles when exposed to denaturation were identified through LC-MS/MS analysis. The pathways derived from bioinformatics analyses were validated by in silico and functional studies. Results: The proteomic profiles of resistant melanoma cells were compared to parental counterparts by taking into account protein folding/unfolding behaviors. Several proteins were found to be involved, with dihydrolipoamide dehydrogenase (DLD) being the only one similarly affected by denaturation in all resistant cell sublines compared to parental ones. DLD expression was observed to be increased in resistant cells by Western blot analysis. Protein modeling analyses of DLD’s catalytic site coupled to in vitro assays with CPI-613, a specific DLD inhibitor, highlighted the role of DLD enzymatic functions in the molecular mechanisms of BRAFi resistance. Conclusions: Our proteomic and structural investigations on resistant sublines indicate that DLD may represent a novel and potent target for overcoming vemurafenib resistance in melanoma cells. 相似文献
29.
30.
Angelo C. Pinto Susan K. Do Prado Raimundo Braz Filho William E. Hull Andras Neszmelyi Gabor Lukacs 《Tetrahedron letters》1982,23(50):5267-5270
With the help of Natural Abundance 13C - 13C Coupling Constants, observed via double quantum coherence, the structural determination of VELLOZIOLONE (1), a new diterpene, has been carried out. 相似文献