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121.
Vinicio Boffi 《Annali di Matematica Pura ed Applicata》1976,108(1):283-295
Sunto. In questa nota si discutono le proprietà funzionali di una classe di equazioni integrali lineari che si incontrano in teoria
del trasporto sia di particelle sia di calore, e si imposta il problema della loro risoluzione per via costruttiva.
A Dario Graffi nel suo 70° compleanno
Entrata in Redazione il 6 settembre 1975. 相似文献
Summary The functional properties of a class of linear integral equations governing various transport phenomena are discussed in this note. A constructive method relevant to their solution is also presented.
A Dario Graffi nel suo 70° compleanno
Entrata in Redazione il 6 settembre 1975. 相似文献
122.
Vinicio Galasso Giorgio Pellizer Henri Le Bail Giuseppe C. Pappalardo 《Magnetic resonance in chemistry : MRC》1976,8(9):457-460
13C n.m.r. spectra are reported for 1,3-indandione, phthalic anhydride, thiophthalic anhydride, and phthalimide in chloroform-d solution. The 13C chemical shifts have also been calculated by means of Pople's perturbation theory using CNDO/S wave functions; the agreement between theoretical and experimental values is improved when an empirical charge-dependent term is added to the calculated diamagnetic and paramagneitc contributions. 相似文献
123.
Aggarwal R Benedetti F Berti F Buchini S Colombatti A Dinon F Galasso V Norbedo S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(13):3132-3142
Amidase antibody 312d6, obtained against the sulfonamide hapten 4 a that mimics the transition state for hydrolysis of a distorted amide, accelerates the hydrolysis of the corresponding amides 1 a-3 a by a factor of 10(3) at pH 8. The mechanisms of both the uncatalyzed and antibody-catalyzed reactions were studied. Between pH 8 and 12 the uncatalyzed hydrolysis of N-toluoylindoles 1 a and 3 a shows a simple first-order dependence on [OH(-)], while hydrolysis of 3 a is zeroth-order in [OH(-)] below pH 8. The pH profile for hydrolysis of the corresponding tryptophan amide 2 a is more complex due to the dissociation of the zwitterion into an anion with pK(a) 9.74; hydrolysis of the zwitterionic and the anionic form of 2 a both show simple first-order dependence on [OH(-)]. Absence of (18)O exchange between H(2) (18)O/(18)OH(-) and the substrate, a normal SKIE for both 1 a (k(H)/k(D)=1.12) and 3 a (k(H)/k(D)=1.24) and the value of the Hammett constant rho for hydrolysis of p-substituted amides 3 a-e are consistent with an ester-like mechanism in which formation of the tetrahedral intermediate is rate-determining and the amine departs as anion. The 312d6-catalyzed hydrolysis of 3 a was studied between pH 7.5 and 9, and its independence of pH in this range indicates that water is the reacting nucleophile. Hydrolysis of 3 a is only partially inhibited by the sulfonamide hapten, and this indicates that non-specific catalysis by the protein accompanies the specific process. Only the nonspecific process is observed in the hydrolysis of amides 3 with para substituents other than methyl. Binding studies on the corresponding series of p-substituted sulfonamides 5 a-e confirm the high specificity of antibody 312d6 for p-methyl substituted substrates. 相似文献
124.
Vinicio Galasso 《Theoretical chemistry accounts》1983,63(1):35-41
Non-empirical SOS-CI calculations based on Nakatsuji's theory are reported for the nuclear spin-spin coupling constants, (considering all the four spininteractions), magnetic shielding constants and magnetic susceptibilities of all the first- and second-row hydrides. The calculated values, except for 2J(HH), correlate satisfactorily with the available experimental data and with the corresponding CHF results, and prove that the SOS-CI model according to Nakatsuji may be a convenient alternative to the time-consuming CHF procedures in order to get accurate estimates of second-order magnetic properties. 相似文献
125.
Sampedro D Migani A Pepi A Busi E Basosi R Latterini L Elisei F Fusi S Ponticelli F Zanirato V Olivucci M 《Journal of the American Chemical Society》2004,126(30):9349-9359
Protonated Schiff bases (PSBs) of polyenals constitute a class of light-driven switchers selected by biological evolution that provide model compounds for the development of artificial light-driven molecular devices or motors. In the present paper, our primary target is to show, through combined computational and experimental studies, that it is possible to approach the design of artificial PSBs suitable for such applications. Below, we use the methods of computational photochemistry to design and characterize the prototype biomimetic molecular switchers 4-cyclopenten-2'-enylidene-3,4-dihydro-2H-pyrrolinium and its 5,5'-dimethyl derivative both containing the penta-2,4-dieniminium chromophore. To find support for the predicted behavior, we also report the photochemical reaction path of the synthetically accessible compound 4-benzylidene-3,4-dihydro-2H-pyrrolinium. We show that the preparation and photochemical characterization of this compound (together with three different N-methyl derivatives) provide both support for the predicted photoisomerization mechanism and information on its sensitivity to the molecular environment. 相似文献
126.
127.
128.
Vinicio Zanirato Gian P. Pollini Filippo Valente Stefania Fusi Massimo Olivucci 《Tetrahedron》2007,63(23):4975-4982
A cyclopropyl ring-opening/nitrilium ion ring-closing tandem reaction has been conveniently used in an expeditious synthetic approach to light-driven Z/E molecular switches featuring an imine function conjugated to olefin groups that mimics natural protonated Schiff bases. 相似文献
129.
130.
Attractive emulsions near the colloidal glass transition are investigated by rheometry and optical microscopy under shear. We find that (i) the apparent viscosity eta drops with increasing shear rate, then remains approximately constant in a range of shear rates, then continues to decay; (ii) the first normal stress difference N1 transitions sharply from nearly zero to negative in the region of constant shear viscosity; and (iii) correspondingly, cylindrical flocs form, align along the vorticity, and undergo a log-rolling movement. An analysis of the interplay between steric constraints, attractive forces, and composition explains this behavior, which seems universal to several other complex systems. 相似文献