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101.
Migani A Gentili PL Negri F Olivucci M Romani A Favaro G Becker RS 《The journal of physical chemistry. A》2005,109(39):8684-8692
The efficiency of the photochemical ring-opening of chromenes (or benzopyrans) depends on the vibronic transition selected by the chosen excitation wavelength. In the present work, ab initio CASPT2//CASSCF calculations are used to determine the excited-state ring-opening reaction coordinate for 2H-chromene (C) and 2,2-diethyl-2H-chromene (DEC) and provide an explanation for such an unusual mode-dependent behavior. It is shown that excited-state relaxation and decay occur via a multimodal and barrierless (or nearly barrierless) reaction coordinate. In particular, the relaxation out of the Franck-Condon involves a combination of in-plane skeletal stretching and out-of-plane modes, while the second part of the reaction coordinate is dominated exclusively by a different out-of-plane mode. Population of this last mode is shown to be preparatory with respect to both C-O bond breaking and decay via an S(1)/S(0) conical intersection. The observed mode-dependent ring-opening efficiency is explained by showing that the vibrational mode corresponding to the most efficient vibronic transition has the largest projection onto the out-of-plane mode of the reaction coordinate. To support the computationally derived mechanism, we provide experimental evidence that the photochemical ring-opening reaction of 2,2-dimethyl-7,8-benzo(2H)chromene, that similarly to DEC exhibits a mode-dependent photoreaction, has a low ( approximately 1 kcal mol(-1)) activation energy barrier. 相似文献
102.
Giuseppe BifulcoTeresa Caserta Luigi Gomez-Paloma Vincenzo Piccialli 《Tetrahedron letters》2003,44(29):5499-5503
Further studies on the RuO4-catalyzed oxidative polycyclization of isoprenoid polyenes have been carried out. The configuration of the tris-THF product from the oxidation of geranylgeranyl acetate has been determined by a combination of spectral and chemical correlation methods. The oxidation of (E,Z)-farnesyl acetate, synthesized from nerol, has been carried out. This process stops at the first cyclization indicating that an E configuration of the Δ6 double bond is needed for the second cyclization to occur. The results are discussed in comparison with previous knowledge on the related Re(VII) polycyclization of polyenic bis-homoallylic alcohols. 相似文献
103.
Sunto In questa Nota è descritto wn metodo per la determinazione delle soluzioni della seguente equazione condizionale f(x+y) f(x) + f(y) + a implica f(x + y)=f(x) + f(y) dove f:GH, a H e G ed H sono gruppi abeliani qualsiasi. Sono poi determinate esplicitamente le soluzioni nei casi G=(r), G= e G=(p).
Lavoro svolto nell'ambito del G.N.A.F.A.-C.N.R. 相似文献
Lavoro svolto nell'ambito del G.N.A.F.A.-C.N.R. 相似文献
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The renewal of the urban waterfronts has become a major focus of attention for politicians and decision makers in the city’s management programs. The recognition of the patterns that define the waterfronts’ identity is essential to select new strategies of intervention for the environmental recovery. In order to create adequate environments for everyday life within a sustainable development, new links between human senses, human perception and design need to be created. Within this wide approach, the landscape and the soundscape play a significant role and can become a key driving force in the implementation of the changes. New techniques have to be tested to identify the sonic and visual parameters capable to explain the specificity of a waterfront. With this purpose, an artificial neural network (ANN) was developed, and the relative importance of the input variables was evaluated. The collected database was also analysed by multiple linear regression (MLR) to compare the outcomes of both models. The urban waterfront of Naples (Italy) was chosen as case study. The results obtained show that the performance of the neural network is better than the one of the linear regression (rANN = 0.949, rMLR = 0.639). The interpretation of the relative importance method is also quite satisfactory in the ANN. 相似文献
107.
Giancarlo De Santis Luigi Fabbrizzi Maurizio Licchelli Piersandro Pallavicini Angelo Perotti Antonio Poggi 《Supramolecular chemistry》2013,25(2):115-125
Abstract The new ferrocene-containing water-soluble ligands 1 and 2 were synthesized and their protonation and complexation properties toward NiII and CuII studied as a function of pH, by means of potentiometric titration experiments. Electrochemical measurements were performed in aqueous solution on pure 1 and 2 and in the presence of NiII and CuII cations, in the pH range 2–12, allowing us to determine the redox potential values relative to the ferrocene oxidation in the free ligands and in their NiII and CuII complexes. 1 and 2 behave as redox switchable ligands, the former enhancing, the latter decreasing its binding ability upon oxidation of the appended ferrocene function. Besides, the CuII complex of ligand 1 and the NiII complex of ligand 2 behave as two-centre two-electron redox systems, the complexed metal cation being subject to further oxidation to MIII. 相似文献
108.
Dr. Emilio M. Pellegrino Prof. Luigi Cerruti Prof. Elena M. Ghibaudi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4330-4335
The present reflection on the development of research on carbon nanotubes (CNTs) stems from the publication of the report “Realizing the Promise of Carbon Nanotubes” by the US National Nanotechnology Initiative in 2015. The report is a critical assessment of the state‐of‐art of CNT research and highlights some unresolved issues related with this field. Starting from the results of this assessment, we carried out an analysis of the publications’ pool in CNTs and related domains, by exploiting bibliometric tools. We focused on the item of competition/collaboration between disciplines and nations, with the purpose of evaluating the position of chemistry (as a discipline) as well as the position of the main European countries and the European Union (EU) as a whole in the context of CNT research. The results of such analysis outline very clearly the interdisciplinary landscape wherein CNT research is situated and show the highly competitive place occupied by EU in the field. 相似文献
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