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21.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
22.
We present an analytical expression of the Wigner distribution function (WDF) for the bound eigenstates of the rotating Morse oscillator (RMO). The effect of rotational excitation on the WDF on the quantum phase space has been demonstrated. This effect has been visualized by a series of contour diagrams for given rovibrational quantum states. Rotations of the molecule have been proved to qualitatively and quantitatively change the Wigner function. As a result, the most probable distance between atoms in a rotating molecule changes, and depends on the parity of the vibrational quantum number. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
23.
We have been studying the problem of heterogeneity of OH groups in zeolites HY for a long time. The heterogeneity was suggested by the shift of the IR band of OH groups restoring upon ammonia desorption and also by the fact that the band of OH groups forming hydrogen bonds was relatively broad (broader than for homogeneous acidic OH). In the present study we present another important argument for heterogeneity: the splitting of the IR band of free OH and OD groups in a zeolite of Si/Al=8.3 dealuminated by (NH4)2SiF6 treatment. Such a splitting is the best seen in low temperature spectra of OD groups. We found less acidic 3640 cm−1 (AlO)(SiO)2SiO1HAl(OSi)3 and more acidic 3625 cm−1 (SiO)3SiO1HAl(OSi)3 groups. The presence of these two kinds of hydroxyls corresponds to the presence of Si(2Al) and Si(1Al), respectively, detected in 29Si MAS NMR spectra. We also found a small amount of strongly acidic 3599 cm−1 hydroxyls interacting with extraframework Al species. 相似文献
24.
Micha Kijak Anna Zieli ska Charles Chamchoumis Jerzy Herbich Randolph P. Thummel Jacek Waluk 《Chemical physics letters》2004,400(4-6):279-285
Depending on the polarity and protic abilities of the solvent, 2-(2′-pyridyl)pyrrole can exist in either syn or anti rotameric forms. In nonpolar solvents, intramolecular excited state single proton transfer is observed, manifested by the appearance of low-energy tautomeric emission. The solvent-assisted excited state double proton transfer reaction is also detected. DFT calculations confirm low barriers for both single and double proton transfer processes in the lowest excited singlet state and show different character of the tautomerization in both cases: in the intramolecular reaction, mutual approach of two nitrogen atoms plays an important role. 相似文献
25.
The lithium and europium(III) cryptates of a macrobicyclic ligand 1 incorporating the 3,3′-biisoquinoline 2,2′-dioxide 2 have been prepared. The Eu(III) complex [Eu(2)2]Cl3 has also been obtained. These Eu(III) complexes present characteristic 1H-NMR spectra containing markedly shifted resonances. They are strongly luminescent; the emission spectra, quantum yields, and lifetimes have been determined. 相似文献
26.
Bocian W Kawecki R Bednarek E Sitkowski J Pietrzyk A Williamson MP Hansen PE Kozerski L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5776-5787
The binding constants of camptothecin, topotecan and its lactone ring-opened carboxylate derivative to DNA octamers were measured by UV and NMR spectroscopy. The self-association of topotecan (TPT) was also measured. The carboxylate form of TPT binds in the same way as the lactone, but more weakly. Titration of TPT into d(GCGATCGC)2 shows a preferred location stacked onto the terminal G1 base. However, the intermolecular NOEs cannot be reconciled with a single conformation of the complex, and suggest a model of a limited number of conformations in fast exchange. MD calculations on four pairs of starting structures with TPT stacked onto the G1-C8 base pair in different orientations were therefore performed. The use of selected experimental "docking" restraints yielded ten MD trajectories covering a wide conformational space. From a combination of calculated free energies, NOEs and chemical shifts, some of the structures produced could be eliminated, and it is concluded that the data are consistent with two major families of conformations in fast exchange. One of these is the conformation found in a crystal of a TPT/DNA/topoisomerase I ternary complex [Proc. Natl. Acad. Sci. USA 2002, 99, 15 387-15 392]. 相似文献
27.
Yinghong Sheng Jerzy Leszczynski Thuc-Quyen Nguyen Anu Bamgbelu 《Structural chemistry》2007,18(6):827-832
A theoretical study using density functional theory was performed to understand the structure/property relationship of the
cationic conjugated polyelectrolytes, poly[9,9-bis-(6′-N,N,N-trimethylammonium) hexyl] fluorene-alt-4,7-(2,1,3-benzothiadiazole)] (PFBT-X, where X = Br). The torsion angle between the fluorene and benzothiadiazole units in the PFBT monomer was found to substantially affect
the structural and electronic properties of the cationic PFBT monomer. The changes of geometrical parameter, HOMO and LUMO energy levels, and band gap, as well as the absorption maximum
are discussed in terms of the torsion in the PFBT monomer structure. For comparison, its neutral analogue, the monomer of
poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) was also studied. The length of conjugation backbone was also examined. 相似文献
28.
In this work, absorption and fluorescence spectra of protochlorophyllide (Pchlide), as well as its fluorescence lifetime, were investigated in organic solvents having different physical properties. The obtained Pchlide spectral features are discussed in relation to the parameters describing solvent properties (refractive index and dielectric constant) and taking into account the specific solvent-Pchlide interaction. The correlation of Pchlide Qy and Soret absorption bands with solvent polarizability function ((n2 - 1)/(n2 + 2)) has been found; however, the dispersion of the observed points was rather high. A small Stokes shift of a magnitude between 50 and 300 cm(-1) was found, which indicates low sensitivity of Pchlide to nonspecific solvation. The fluorescence decay of Pchlide was single exponential in all the investigated solvents, with the lifetime value ranging from 5.2 ns for dioxane to 3.5 ns for methanol. Dependence of the obtained fluorescence lifetimes on the solvent orientation polarizability, a parameter being the function of both refractive index and dielectric constant, was discussed. In water-methanol mixtures, a further decrease of the fluorescence lifetime was observed, giving values of 2.9 ns for 25% methanol. Double-exponential decay of Pchlide fluorescence was found for Pchlide in a solution of 15% methanol with the lifetimes of 4.5 +/- 0.5 ns and 1.2 +/- 0.3 ns and in pure water with the lifetimes of 2.5 +/- 0.5 ns and 0.4 +/- 0.1 ns. The obtained results are discussed in relation to spectroscopic properties of Pchlide in vivo. 相似文献
29.
A theoretical analysis of the concept of lifetime and mean life of unstable elementary particles is presented. New analytic formulas for lifetime and mean life as a function of decay width and the mass of unstable particle are derived for Breit-Wigner and Matthews-Salam energy distributions. It is demonstrated that, for unstable particles with a larger width or decay energy threshold, the deviation from the generally accepted mean life
m =
–1
is significant. The behavior of the decay law P(t) for small times is analyzed, and it is shown that the Breit-Wigner distribution violates the condition P(t = 0) = 0, whereas the Matthews-Salam distribution satisfies it. 相似文献
30.
We prove that certain two-point Padé approximants occupying the diagonal of the Padé table form monotone sequences of lower and upper bounds uniformly converging to a Stieltjes function. The results can be applied to the theory of inhomogeneous media for the calculation of the bounds on the effective transport coefficients of heterogeneous materials. 相似文献