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71.
72.
Jagoda M Warzeska S Pritzkow H Wadepohl H Imhof P Smith JC Krämer R 《Journal of the American Chemical Society》2005,127(43):15061-15070
For a number of phosphoryltransfer enzymes, including the exonuclease subunit of DNA polymerase I, a mechanism involving two-metal ions and double Lewis-acid activation of the substrate, combined with leaving group stabilization, has been proposed. Inspired by the active site structure of this enzyme, we have designed as a synthetic phosphoryl transfer catalyst the dicopper(II) macrocyclic complex LCu(2). Crystal structures of complexes [(L)Cu(2)(mu-NO(3))(NO(3))](NO(3))(2) (1), [(L)Cu(2)(mu-CO(3))(CH(3)OH)](BF(4))(2) (2), and [(L)Cu(2)(mu-O(2)P(OCH(3))(2))(NO(3))](NO(3))(2) (3) illustrate various possibilities for the interaction of oxoanions with the dicopper(II) site. 1 efficiently promotes the transesterification of dimethyl phosphate (DMP) in CD(3)OD, k(cat) = 2 x 10(-)(4) s(-)(1) at 55 degrees C. 1 is the only available catalyst for the smooth transesterification of highly inert simple dialkyl phosphates. From photometric titrations and the pH dependence of reactivity, we conclude that a complex [(L)Cu(2)(DMP)(OCH(3))](2+) is the reactive species. Steric bulk at the -OR substituents of phosphodiester substrates O(2)P(OR)(2)(-) drastically reduces the reactivity of 1. This is explained with -OR leaving group stabilization by Cu coordination, an interaction which is sensitive to steric crowding at the alpha-C-atom of substituent R. A proposed reaction mechanism related to that of the exonuclease unit of DNA polymerase I is supported by DFT calculations on reaction intermediates. The complex [(L)Cu(3)(mu(3)-OH)(mu-CH(3)O)(2)(CH(3)CN)(2)](ClO(4))(3) (4) incorporates a [Cu(OH)(OCH(3))(2)(CH(3)CN)(2)](-) complex anion, which might be considered as an analogue of the [PO(2)(OCH(3))(2)(OCD(3))](2)(-) transition state (or intermediate) of DMP transesterification catalyzed by LCu(2). 相似文献
73.
Electroactive conducting copolymers of aniline (ANI) and o-aminophenol (OAP) and two-layered poly(o-aminophenol) (POAP)/polyaniline (PANI) composites were prepared in aqueous acidic solution by electrode potential cycling.
Copolymerization was carried out at different feed concentrations of OAP and ANI on a gold electrode. A strong inhibition
of electropolymerization was found at a high molar fraction of OAP in the feed. The copolymers showed good adherence on the
electrode surface and gave a redox response up to pH=10.0. Two transitions were observed in the in situ conductivities of
the copolymers (as with PANI), but the conductivities were lower by 2.5–3 orders of magnitude as compared to PANI. Electrosynthesis
of PANI on POAP modified electrodes showed copolymer formation after reaction initiation and finally formation of a PANI layer
at the copolymer/solution interface. The ‘memory effect’ of the bilayer structures of both polymers was discussed in terms
of protonation/deprotonation and anion consumption taking place during redox processes of both polymers. 相似文献
74.
Rigler R 《Electrophoresis》2002,23(5):805-808
The behavior of negatively charged single rhodamine-labeled molecules excited to fluorescence in confocal volume elements has been investigated in oscillating voltage gradients between 1 and 15 kV/cm. The effective charge of rhodamin labeled deoxy-uridine triphosphate (Rh-dUTP) is dependent on the field strength applied and likely is due to differences in the screening by counter ions. It can be shown that the attractive forces generated by an oscillating dipole can increase the concentration of Rh-dUTP by a factor 2. Likewise a substantial increase of concentration can be obtained for Rh-labeled DNA molecules when linear voltage gradients are applied. The importance for diagnostic analysis at the single molecule level is discussed. 相似文献
75.
76.
Petra Spitzer Bruno Rossi Yves Gaignet Stéphane Mabic Uwe Sudmeier 《Accreditation and quality assurance》2005,10(3):78-81
There is currently a major issue with the calibration of conductivity meters used for high purity water: the lack of availability of a reference material or reference methods for low conductivity ranges (conductivity below 1 S cm–1 at 25.0 °C, resistivity >1 M cm at 25.0 °C). This paper describes the current status of conductivity measurements in high purity water. A new and improved approach, currently being investigated, should allow us to make the calibration of conductivity meters used for low conductivity ranges traceable to the SI.Milipore, Milli-Q and Elix are registered trademarks of Millipore Corporation. 相似文献
77.
The ZnCl2 catalyzed reaction of p-methoxybenzyl chloride with alkenes yields the 1:1 addition products 3, which are converted into the γ-lactones 4 via Ru(VIII) catalyzed oxidative degradation of the aromatic ring. 相似文献
78.
79.
The model of two interacting ethylene molecules having D
2h symmetry was studied using generalized Hückel method. The validity of - separation was tested on this model. The general character of the ground state and lower lying excited states of the model was discussed and the implications drawn concerning transannular interaction and excimer formation. The values obtained for the dissociation energy of the first excited state of our model and corresponding equilibrium intermolecular distance are of right order of magnitude.
Zusammenfassung Mittels der verallgemeinerten Hückel-Methode wurde das Modell von zwei Äthylenmolekülen mit der Symmetrie D 2h studiert. An diesem Modell wurde die Gültigkeit der - -Separation geprüft. Der allgemeine Charakter des Grundzustandes und der niedriger liegenden angeregten Zustände des Modells wird erörtert und die Folgerungen in Bezug auf transannulare Wechselwirkung und Excimer-Entstehung diskutiert. Die erhaltenen Werte für die Dissoziationsenergie des ersten angeregten Zustandes von unserem Modell und den entsprechenden intermolekularen Gleichgewichtsabstand haben die richtige Größenordnung.
Résumé Le modèle à symétrie D 2h de deux molécules d'éthylène en interaction a été étudié en utilisant la méthode généralisée de Hückel. On a examiné la validité de la séparation - sur ce modèle. Le caractère général de l'état fondamental et celui des états excités inférieurs du modèle furent discutés et on a fait des déductions sur l'interaction transannulaire et sur la formation d'«excimères». Les valeurs obtenues pour l'énergie de dissociation du premier état excité de notre modèle et la distance intermoléculaire d'équilibre corréspondante ont l'ordre de magnitude correct.相似文献
80.
Synthesis of 15-Hydroxy[9]metacyclophane 3-(1-Nitro-2-oxocyclododecyl)propanal ( 1 ) was converted to 15-hydroxy[9]metacyclophane ( 3 ) on two different routes. In the first case the internal aldol reaction product of 1 was treated with K2CO3/THF to give 3 in 29 % yield with regard to cyclododecanone. Alternatively, the aldehyde 1 reacted with a primary amine to form e.g. 4 which gave 3 in the presence of CH3I/K2CO3 in 48 % yield. 相似文献