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161.
The silver catalyzed oxidative decarboxylation of carboxylic acids by aroylperoxides, percarbonates and perborate provides new sources of alkyl radicals useful for selective substitution of lepidine. 相似文献
162.
The problem of defining and determinating the shear centre is present in the literature since the first decades of this century.
It soon interlaced with the definition of the twist centre and their ways became unextricable in the following decades. A
number of researchers dealt with this subject meeting with variable issues, yet in the authors' opinion it seems of some interest
to run through it again. In this paper a general survey of the literature is performed and the two definitions of the shear
centre (here named kinematic and energetic) are compared. It is remarked how the energetic definition for the shear centre
makes it coincide with a suitably chosen twist centre. An example is given to show that the two definitions generally fail
to provide the same place even for simple cross sections. It is shown that the two definitions provide the same place, using
standard approximate formul?, in the case of thin-walled mono-connected sections with regularly varying thickness and two-connected
sections with constant thickness. As a new result, it will be shown that the two definitions of shear centre do not provide
the same place for thin-walled sections with connection higher than two even in the trivial case of uniform thickness; an
example is given.
Received November 25, 1997 相似文献
163.
Antonino Corsaro Ugo Chiacchio Giancarlo Perrini Pierluigi Caramella Franca Marinone Albini 《Journal of heterocyclic chemistry》1989,26(6):1691-1699
A study on the acetylation and benzoylation of title compounds by quenching the corresponding 4-carbanions with acyl chlorides or esters is reported. The obtained ketones are formed as minor regioisomeric adducts in the cycloadditions of benzo and mesitonitrile oxide to methyl and phenyl vinyl ketone. The quenching with methyl chloroformate was also examined as a possible convenient route to 4-methoxycarbonyl-3-aryl-4,5-dihydroisoxazoles. 相似文献
164.
165.
The ground state of CH2Li? and CH2Be molecules has been investigated by an SCF calculation using a contracted Gaussian basis set. Only for the second system a bound state with respect to the ground states of the molecular fragments has been found. 相似文献
166.
167.
Kang H Facchetti A Jiang H Cariati E Righetto S Ugo R Zuccaccia C Macchioni A Stern CL Liu Z Ho ST Brown EC Ratner MA Marks TJ 《Journal of the American Chemical Society》2007,129(11):3267-3286
This contribution details the synthesis and chemical/physical characterization of a series of unconventional twisted pi-electron system electro-optic (EO) chromophores. Crystallographic analysis of these chromophores reveals large ring-ring dihedral twist angles (80-89 degrees) and a highly charge-separated zwitterionic structure dominating the ground state. NOE NMR measurements of the twist angle in solution confirm that the solid-state twisting persists essentially unchanged in solution. Optical, IR, and NMR spectroscopic studies in both the solution phase and solid state further substantiate that the solid-state structural characteristics persist in solution. The aggregation of these highly polar zwitterions is investigated using several experimental techniques, including concentration-dependent optical and fluorescence spectroscopy and pulsed field gradient spin-echo (PGSE) NMR spectroscopy in combination with solid-state data. These studies reveal clear evidence of the formation of centrosymmetric aggregates in concentrated solutions and in the solid state and provide quantitative information on the extent of aggregation. Solution-phase DC electric-field-induced second-harmonic generation (EFISH) measurements reveal unprecedented hyperpolarizabilities (nonresonant mubeta as high as -488,000 x 10(-48) esu at 1907 nm). Incorporation of these chromophores into guest-host poled polyvinylphenol films provides very large electro-optic coefficients (r(33)) of approximately 330 pm/V at 1310 nm. The aggregation and structure-property effects on the observed linear/nonlinear optical properties are discussed. High-level computations based on state-averaged complete active space self-consistent field (SA-CASSCF) methods provide a new rationale for these exceptional hyperpolarizabilities and demonstrate significant solvation effects on hyperpolarizabilities, in good agreement with experiment. As such, this work suggests new paradigms for molecular hyperpolarizabilities and electro-optics. 相似文献
168.
Enrica Rosato Martina Bonelli Marcello Locatelli Ugo de Grazia Angela Tartaglia Fabio Savini Cristian DOvidio 《Molecules (Basel, Switzerland)》2021,26(11)
Currently, forensic research is multidisciplinary with new methods and parameters useful to define the cause and time of death as well as survival/agony times. The identification of biochemical markers able to estimate agonal period has been studied by many forensic researchers. It is known that the estimation of agonal time in different types of death is not always easy, hence our interest in literature’s data. The studies analyzed in this review confirm the important role of thanatobiochemistry for the estimation of survival times. Regardless of the death cause, the survival/agony time between the primary event and death influences markers concentrations in biological samples (e.g., blood, urine, cerebrospinal fluid). Different biomarkers can be used for qualitative evaluations in deaths with short and long agony (e.g., C-reactive protein, ferritin, GFAP, etc.). Instead, the quantitative interpretation showed limits due to the lack of reference cut-offs. Thanatobiochemistry is a useful tool to confirm what emerged from autopsies findings (macroscopic and histological analysis), but further studies are desirable to confirm the evidence emerging from our review of the literature. 相似文献
169.
Cariati E Forni A Biella S Metrangolo P Meyer F Resnati G Righetto S Tordin E Ugo R 《Chemical communications (Cambridge, England)》2007,(25):2590-2592
As a function of the ability of the solvent to behave as acceptor of halogen bonding, the NLO-phores under study give rise to microbeta(lambda) values ranging from +192 x 10(-48) esu to -465 x 10(-48) esu. 相似文献
170.
Large-eddy simulations were carried out to study the effects of surface roughness on a plane wall-jet using the Lagrangian dynamic eddy-viscosity subgrid-scale model, at Re = 7500 (based on the jet bulk velocity and height). Results over both smooth and rough surfaces were validated by experimental data at the same Reynolds number. As the jet is injected into the still environment, large-scale rollers are generated in the shear layer between the high-momentum fluid of the jet and the surrounding and are convected downstream with the flow. To understand the extent to which the outer-layer structures modify the flow in the inner layer and the extent to which the effect of roughness spreads away from the wall, both instantaneous and mean flow fields were investigated. The results revealed that, for the Reynolds number and roughness height considered in this study, the effect of roughness is mostly confined to the near-wall region of the wall jet. There is no structural difference between the outer layer of the wall jet over the smooth and rough surfaces. Roughness does not affect the size of the outer-layer structures or the scaling of the profiles of Reynolds stresses in the outer layer. However, in the inner layer, roughness redistributes stresses from streamwise to wall-normal and spanwise directions toward isotropy. Contours of joint probability-density function of the streamwise and wall-normal velocity fluctuations at the bottom of the logarithmic region match those of the turbulent boundary layer at the same height; while the traces of the outer-layer structure were detected at the top of the logarithmic region, indicating that they do not affect the flow very close to the wall, but still modify a major portion of the inner layer. This modification must be taken into consideration when the inner layer of a wall jet is compared with the conventional turbulent boundary layer. 相似文献