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91.
Naringenin is a natural widespread flavanone occurring in different foodstuffs that presents several important biological activities. Although its properties are well documented, its mechanisms of action are still controversial. The present article reports a conformational analysis of naringenin, using the semiempirical AM1 and ab initio methods, at the Hartree–Fock level of theory. The 3-21G, 3-21G*, 6-31G, and 6-31G** basis sets were used. The electron correlation effects were included through the Møller–Plesset second-order perturbation theory. The solvation of naringenin has been investigated through the standard SCRF, the supermolecule (SM), and the combined SM/SCRF models. The results have shown that there are two degenerate forms of naringenin, differing mainly by the orientation of a hydroxyl group (C4—OH). The energy barrier for the interconversion between them is ca. 6 kcal.mol–1, suggesting some conjugation between the -system of the aromatic B ring and the hydroxyl group (C4—OH). 相似文献
92.
Wagner HP Pepich BV Frebis CP Hautman DP Munch DJ Jackson PE 《Journal of chromatographic science》2001,39(6):255-259
The development of the U.S. Environmental Protection Agency (EPA) Method 317.0 is initiated to provide a sufficiently sensitive and fundamental technique for the compliance monitoring of trace levels of bromate in drinking water. After a comparative evaluation of Method 317.0 and elimination of a chlorite interference, this method is tested by a collaborative study in order to determine the precision and bias of the method and evaluate its potential role as a future compliance-monitoring method for inorganic disinfection by-products (DBPs) and trace bromate. This technique provides a practical method for future compliance monitoring for all of the inorganic oxyhalide DBPs including trace concentrations of bromate. 相似文献
93.
Cacciapaglia R Casnati A Mandolini L Reinhoudt DN Salvio R Sartori A Ungaro R 《The Journal of organic chemistry》2005,70(2):624-630
The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst-substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal > 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism. 相似文献
94.
Mandrioli R Musenga A Ferranti A Lasaponara SS Fanali S Raggi MA 《Journal of separation science》2005,28(9-10):966-972
A micellar electrokinetic chromatographic method was developed and applied for the first time to the separation and quantification of the main components of cloves, namely eugenol and beta-caryophyllene. The analytes were separated in less than ten minutes in an unmodified fused silica capillary (effective length: 40.0 cm) using a background electrolyte composed of 25 mM carbonate buffer (pH 10.0) and 60 mM sodium dodecylsulfate. Analyte concentrations were determined in clove oil and in methanolic clove extracts after simple sequential dilution with methanol and background electrolyte, and the resulting electropherograms showed no interference due to other components. Precision assays gave satisfactory results, with mean standard deviation of peak areas lower than 4.7% (lower than 1.5% for migration times). The eugenol content of a commercial clove oil was about 70% (RSD% = 3.2), while that of beta-caryophyllene was about 15% (RSD% = 4.2); in clove extracts, on the other hand, eugenol was approximately 15% (RSD% = 4.7) and beta-caryophyllene 4% (RSD% = 5.1). Accuracy was also good (mean recovery >98%). 相似文献
95.
Peter Wagner 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1984,35(5):723-727
Zusammenfassung Es wird eine Darstellung einer Fundamentallösung des OperatorsP()=Q()2–(c1)2m
durch Fundamentallösungen der OperatorenQ()±(c1)
m
angegeben. Als Anwendung berechnen wir die Singularitätenfunktionen der gespannten Platte und der Kreiszylinderschale.
Summary A method is given, which allows to derive a fundamental solution of the operatorP()=Q()2–(c1)2m from some fundamental solutions of the operatorsQ()±(c1) m . As an application we easily obtain the singular solutions of the unidirectionally stretched plate and of the circular cylindrical shell.相似文献
96.
Ingrid Fischler Rosi Wagner Ernst A.Koerner Von Gustorf 《Journal of organometallic chemistry》1976,112(2):155-165
The photochemical reaction of the trinuclear complex Fe3(CO)10NSi(CH3)3 under hydrogen leads to substitution of the bridging carbonyl group by two hydrogens. The resulting complex H2Fe3(CO)9NSi(CH3)3 acts as a catalyst in the photochemical hydrogenation of olefins and dienes. 相似文献
97.
Laura Gagliardi Giorgio Orlandi Fernando Bernardi Alessandro Cembran Marco Garavelli 《Theoretical chemistry accounts》2004,111(2-6):363-372
In the present paper we report the results of a multiconfigurational computational study on potential-energy curves of azobenzene along the NN twisting to clarify the role of this coordinate in the decay of the S2(*) and S1(n*) states. We have found that there is a singlet state, S3 at the trans geometry, on the basis of the doubly excited configuration n2*2, that has a deep minimum at about 90° of twisting, where it is the lowest excited singlet state. The existence of this state provides an explanation for the short lifetime of S2(*) and for the wavelength-dependence of azobenzene photochemistry. We have characterized the S1(n*) state by calculating its vibrational frequencies, which are found to correspond to the recently observed transient Raman spectrum. We have also computed the potential-energy curve for the triplet T1(n*) at the density functional theory B3LYP level, which indicates that in this state the isomerization occurs along the twisting coordinate.Acknowledgement The financial support from MIUR (project Modellistica delle proprietà spettroscopiche di sistemi molecolari complessi funds ex 60% and project Dinamiche molecolari in sistemi di interesse chimico funds ex 40%), from the University of Bologna (Funds for Selected Research Topics) is gratefully acknowledged.Contribution to the Jacopo Tomasi Honorary Issue 相似文献
98.
Alessandro Ferrali 《Tetrahedron letters》2004,45(27):5271-5274
A δ-valerolactam-derived vinyl triflate has been converted into the corresponding vinyl boronate by Pd-catalyzed coupling with bis(pinacolato)diboron, which results in an umpolung. This boronate efficiently couples under Pd catalysis with aryl and heteroaryl bromides to give the corresponding 2-substituted piperidines in excellent yields. 相似文献
99.
Celestino Angeli Renzo Cimiraglia Maurizio Persico Alessandro Toniolo 《Theoretical chemistry accounts》1997,98(1):57-63
We discuss the “three class” approximation to full multireference perturbation CI, which greatly reduces the computational
effort by restricting the summation of diagrams to determinants belonging to a subspace of the zero-order space. In the framework
of the CIPSI algorithm, we propose a new extrapolation procedure allowing recovery of the full “two class” results. The new
procedure is applied to complete active spaces (CAS) and to individually selected zero-order spaces. Comparison with a full
two class calculation on a CAS shows a reduction of computer time of one or two orders of magnitude in the tests presented
here, with an accuracy in the order of 0.1 kcal/mol. Our procedure can thus compete with the CASPT2 algorithm, specifically
conceived to deal with CAS. In the case of selected zero-order spaces, the speed-up is less dramatic but the method still
retains its advantages.
Received: 12 June 1997 / Accepted: 31 July 1997 相似文献
100.
2,3-Bis(ethynyl)-3-hydroxy-camphorsultam was converted in one step into a novel tetracyclic cyclopentenone derivative, in an unprecedented platinum-catalysed cascade reaction. In the course of this reaction, cyclisation of the alkynes takes place, together with a ring expansion of the camphor skeleton and 1,2-migration of an oxygen atom. The structure of the unexpected product was analysed in detail by one- and two-dimensional NMR spectroscopy, and validated with the help of quantum mechanical calculations (B3LYP/6-31G∗∗ and B3LYP/6-31+G(2df)) of the IR vibrational frequencies and the 1H and 13C isotropic chemical shifts. 相似文献