کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5376984 | 1504334 | 2006 | 13 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Theoretical and experimental studies on the molecular and electronic structures of cytisine and unsaturated keto-sparteines
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
![عکس صفحه اول مقاله: Theoretical and experimental studies on the molecular and electronic structures of cytisine and unsaturated keto-sparteines Theoretical and experimental studies on the molecular and electronic structures of cytisine and unsaturated keto-sparteines](/preview/png/5376984.png)
چکیده انگلیسی
Density functional theory calculations with the B3LYP hybrid functional have been performed to determine the equilibrium structures of cytisine, N-methylcytisine, multiflorine, 5,6-didehydromultiflorine, anagyrine, thermopsine, 5,6-didehydrolupanine, and aphyllidine. These molecules, except cytisine, multiflorine, and aphyllidine, exhibit a marked preference for one conformation with the ring C chair. Cytisine, which also adopts the ring C chair, is predicted to exhibit the endo/exo conformational equilibrium of the N-H group in the gas phase or solution. Multiflorine is instead found to exist as a mixture of C-boat and C-chair conformers in the gas phase or solution. The most stable (C-chair) conformer of aphyllidine shows a marked conformational flexibility, with the exo and endo wings of ring A being nearly isoenergetic. The electronic structures of these quinolizidine alkaloids have been studied by measuring and calculating significant features of their NMR and photoelectron spectra. In particular, a representative set of NMR chemical shifts and nuclear spin-spin coupling constants, calculated by means of DFT formalisms, compares favourably with experiment. Notably, the repercussion of stereoelectronic hyperconjugative effects on Îδ(Heq/Hax) and Î1J(CHeq/CHax) of the ãN-CO- groups is correctly accounted for by the DFT results. Based on ab initio outer valence Green's function calculations, a reliable interpretation of the uppermost bands in the photoelectron spectra has been advanced. The theoretical results indicate a complex interaction of the n(N), n(O), Ï(N), Ï(CO), and Ï(CC) chromophores. The lowest-energy conformations of all compounds allow a consistent interpretation of the photoelectron spectra. The conformational equilibrium in the gas phase is partially revealed by the photoelectron spectrum of multiflorine but not by that of cytisine. The single-crystal X-ray structure was also determined for anagyrine hydrochloride hydrate.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Chemical Physics - Volume 325, Issues 2â3, 20 June 2006, Pages 365-377
Journal: Chemical Physics - Volume 325, Issues 2â3, 20 June 2006, Pages 365-377
نویسندگان
V. Galasso, A.K. PrzybyÅ, V. Christov, B. KovaÄ, F. Asaro, E. Zangrando,