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101.
C. Etzlstorfer H. Falk E. Mayr S. Schwarzinger 《Monatshefte für Chemie / Chemical Monthly》1996,127(12):1229-1237
Summary The strongly enhanced acidity of the bay hydroxyl group as compared to the respectiveperi hydroxyl groups of fringelite D, hypericin, and stentorin could be rationalized on the basis of a vinylogous carboxylic acid and was nicely corroborated by semiempirical calculations of the AM1 type. Experimental data obtained from several independent experimental methods, like polarized absorption spectroscopy, hole burning, and isotope effects, as well as from semiempirical AM1 and 6–31G levelab initio calculations conclusively pointed to dissymmetrical hydrogen bonding systems in both theperi andbay regions of the correspondingbay phenolate ions.
Zu Acidität und Wasserstoffbrückenbindung von Hydroxyphenanthroperylenchinonen wie Fringelit D, Hypericin und Stentorin
Zusammenfassung Die stark erhöhte Acidität der bay-Hydroxylgruppen gegenüber jener derperi-Hydroxylgruppen von Fringelit D, Hypericin und Stentorin läßt sich auf der Basis einer vinylogen Carbonsäure verstehen und wurde auch durch semiempirische Rechnungen vom AM1-Typ erhärtet. Daten aus unabhängigen Experimenten wie Polarisationsspektroskopie, Lochbrennen und Isotopeneffekte sowie semiempirische AM1- undab initio-Rechnungen auf 6–31G Niveau belegen ein unsymmetrisches Wasserstoffbrückenbindungssystem sowohl für denperi-als auch denbay-Bereich der entsprechendenbay-Phenolationen.相似文献
102.
Edwin Weber Orm Hager Concepcion Foces-Foces Antonio L. Llamas-Saiz 《Journal of inclusion phenomena and macrocyclic chemistry》1999,34(2):199-220
New chiral host compounds based on mandelic acid derivatives having methyl (6a, b and 8a, b) or bromo substituents (7a, b) attached to the phenyl ring of mandelic acid and involving additional aromatic groups were synthesized. The inclusion properties of both the racemic and the optically resolved host species are reported, including solvent co-crystallization as well as chiroselective and vapour sorptive inclusion. The structures of the free racemic host compound 6b and of the DMSO inclusion compounds of optically resolved and racemic 8 (8a and 8b, respectively) have been determined by X-ray analysis. Enantiomeric pairs of molecules in 6b form centro-symmetric dimers by mutual hydrogen bonding of one hydroxyl group while the other is involved in O-–H ... interactions. The guest molecules in the DMSO complexes of 8a and 8b are bound via hydrogen bonds to two host molecules related by translation along crystallographic axes. Parallels to previous hosts of this type are drawn. 相似文献
103.
A regular polyhedron is isomorphic to a cluster on which every face has same number of bonds and every atom has an equal number of coordinating atoms. A general strategy for generating the eigenvectors and the eigenvalues of regular polyhedra is given. Not sign analyses are also performed on the eigenvectors of regular polyhedra. The results provide us a quick way to grasp the topological feature of the electronic structure of clusters having interesting topology. 相似文献
104.
在电极袭面反应物浓度均匀的近似假设下,得到了微圆盘电极上暂态可逆反应的一般解.然后利用该一般解得到了微圆盘电极上耦合一级均相反应的可逆电极反应CE、EC、EC′和ECE 的稳态电流计算公式. 相似文献
105.
Ab initio supermolecular SCF calculations at the STO-3G level are reported for the diacetylene-hydrogen fluoride complexes. The reverse
σ-complex is predicted to have somewhat higher stability and H-bond strength than the π-complexes. 相似文献
106.
Nils Siegbahn Mats-Olle Maånsson Klaus Mosbach 《Applied biochemistry and biotechnology》1987,12(2):91-105
A soluble, bifunctional enzyme complex has been prepared by crosslinking lactate dehydrogenase and alcohol dehydrogenase with
glutaraldehyde. The crosslinking was performed on a solid phase while the active sites of alcohol dehydrogenase and lactate
dehydrogenase were held adjacent to one another with the aid of a bis-NAD analog. Subsequently, the enzyme complex was released
from the solid phase. The soluble enzyme complex was then purified by using NAD-Sepharose as an affinity adsorbent. Based
on gel filtration experiments, the complex was estimated to consist of one of each dehydrogenase.
By using a third enzyme, lipoamide dehydrogenase, which competes with lactate dehydrogenase for NADH produced by alcohol dehydrogenase,
the effect of site-to-site orientation was studied. It was found that about 83% of the NADH produced by alcohol dehydrogenase
was oxidized by site-to-site oriented lactate dehydrogenase compared to a figure of only about 61% obtained in an identical
system of separate enzymes. This indicates that given two alternative routes, the preference for the one to lactate dehydrogenase
over the one to lipoamide dehydrogenase is enhanced when lactate dehydrogenase and alcohol dehydrogenase are site-to-site
oriented. 相似文献
107.
Complexes of W(CO)(5) with neutral diatomic pnictogen ligands N(2), P(2), As(2), Sb(2), and Bi(2) and anionic Group 14 ligands Si(2) (2-), Ge(2) (2-), Sn(2) (2-), and Pb(2) (2-) coordinated in both side-on and end-on fashion have been optimized by using density functional theory at the BP86 level with valence sets of TZP quality. The calculated bond energies have been used to compare the preferential binding modes of each respective ligand. The results were interpreted by analyzing the nature of the interaction between the ligands and the metal fragment using an energy partitioning method. This yields quantitative information regarding the strength of covalent and electrostatic interactions between the metal and ligand, as well as the contributions by orbitals of different symmetry to the covalent bonding. Results show that all the ligands studied bind preferentially in a side-on coordination mode, with the exception of N(2), which prefers to coordinate in an end-on mode. The preference of the heavier homologues P(2)-Bi(2) for binding in a side-on mode over the end-on mode in the neutral complexes [(CO)(5)WE(2)] comes mainly from the much stronger electrostatic attraction in the former species. The energy difference between the side-on and end-on isomers of the negatively charged complexes with the ligands Si(2) (2-), Ge(2) (2-), Sn(2) (2-), and Pb(2) (2-) is much less and it cannot be ascribed to a particular bonding component. 相似文献
108.
Paolo Samorí Silvia Pieraccini Stefano Masiero Gian Piero Spada Giovanni Gottarelli Jürgen P. Rabe 《Colloids and surfaces. B, Biointerfaces》2002,23(4):283-288
We report a tapping mode scanning force microscopy investigation on the growth from solutions of a lipophilic deoxiguanosine derivative on the basal plane of a muscovite mica surface. By varying the chemical composition of the substrate surface it is possible to drive the self-assembly towards either layered thin films, which are very likely to consist of guanosine quartets, or nanoribbons, comprising hydrogen bonded networks. Both these two architectures, which are peculiar to the guanine base itself, are of notable importance for the fabrication of molecular nanowires. Moreover, the first arrangement provides evidence that the guanosine is able to behave as ionophore, thus, suggesting its utilization in the development of solid-state ion selective sensors. 相似文献
109.
110.
O. D. Bonner 《Journal of solution chemistry》1980,9(11):877-884
Osmotic and activity coefficients, determined from isopiestic measurements, are presented for aqueous solutions of eight tetramethylguanidinium salts. It is proposed that both hydronium and tetramethylguanidinium ions are capable of forming stable ion pairs with many anions by means of bridged hydrogens forming six-membered rings and that these ion pairs are stable in rather dilute aqueous solutions. 相似文献