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11.
Inspired by the concept of multivalency and in pursuit of ever more intricate artificial molecular machines, we investigated the strict self-assembly of a triply threaded two-component superbundle, starting from a tritopic receptor in which three benzo[24]crown-8 macrorings are fused onto a triphenylene core and a trifurcated trication wherein three bipyridinium units are linked 1,3,5 to a central benzenoid core. The result of the investigation was quite unexpected and surprising. It transpired that the rapid formation of a doubly threaded two-component complex was followed by an extremely slow conversion (a week at 253 K in CD3COCD3 to reach equilibrium) of this kinetically controlled product into a thermodynamically controlled one, namely a triply threaded two-component superbundle. This intriguing observation begs the question: are there instances in nature where multivalency is expressed as a kinetically controlled process, prior to an equilibrium state being reached, and if so, what are the biological implications, if any? 相似文献
12.
The purpose of this paper was to investigate the use of limited sets of Gaussian functions as bases to calculate dissociation and activation energies. Gaussian functions have the principal advantage that they lead to integrals that can be performed analytically, even when explicit correlation terms are introduced.Calculations were performed on H2 and linear H3 using a restricted 1s-type Gaussian basis, and direct correlation factors were introduced into the wave function in both cases. The best result for the dissociation energy of H2 was 105.1 kcal/mole. However, the activation energy of the hydrogen atom-hydrogen molecule exchange reaction was calculated to be 15.8 kcal/mole.
S.J.F. wishes to express his gratitude to Pembroke College, Cambridge, for the financial assistance they gave him. 相似文献
Zusammenfassung Die Anwendungsmöglichkeit von Basissätzen einer beschränkten Zahl von Gaußfunktionen zur Berechnung von Dissoziations- und Aktivierungsenergien wird untersucht. Der Hauptvorteil bei der Verwendung von Gaußfunktionen besteht darin, daß sie auf Integrale führen, die analytisch ausgewertet werden können, sogar im Falle, daß explizite Korrelationsanteile in den Funktionen enthalten sind.Für H2 und lineares H3 wurde eine eingeschränkte Gaußfunktionenbasis vom 1s-Typ unter Einschluß expliziter Korrelationsanteile verwendet. Das beste Ergebnis für die Dissoziationsenergie des H2 beträgt 105,1 kcal/mol. Dagegen ergibt sich für die Aktivierungsenergie der Austauschreaktion Wasserstoffatom-Wasserstoffmolekül ein Wert von 15,8 kcal/mol.
S.J.F. wishes to express his gratitude to Pembroke College, Cambridge, for the financial assistance they gave him. 相似文献
13.
Leung KC Aricó F Cantrill SJ Stoddart JF 《Journal of the American Chemical Society》2005,127(16):5808-5810
The versatility and efficiency of dynamic covalent chemistry (DCC) has been exploited in the convergent synthesis of mechanically interlocked dendrimers that are based upon the mutual recognition expressed between secondary dialkylammonium ions and crown ether-like macrocycles. Reversible imine bond formation is employed to clip two acyclic fragments, one of them a diformylpyridine unit bearing a dendritic side chain, and the other a complementary dianiline in the shape of the di(o-aminophenyl)ether of tetraethylene glycol, around each arm of a tritopic trisammonium ion core, thereby affording a branched [4]rotaxane. This template-directed strategy has been demonstrated to work in very high yields (>90%) with successive generations (G0-G2) of a modified Fréchet-type dendritic wedge attached to the 4-position of the diformylpyridine unit. Reduction of these dynamic dendritic systems is achieved upon treatment with borane.THF and results in kinetically stable compounds. The inherent modularity of the overall process should allow for the rapid and straightforward access to many other analogous mechanically interlocked systems in which either the branched core or the dendritic periphery can be modified to suit the needs of any given application of these molecules. Indeed, the dynamic nature of the initial thermodynamically mediated assembly could be utilized in order to amplify particular products from a potential library as a result of a selective recognition process. 相似文献
14.
15.
Jones AK Lamle SE Pershad HR Vincent KA Albracht SP Armstrong FA 《Journal of the American Chemical Society》2003,125(28):8505-8514
The cycling between active and inactive states of the catalytic center of [NiFe]-hydrogenase from Allochromatium vinosum has been investigated by dynamic electrochemical techniques. Adsorbed on a rotating disk pyrolytic graphite "edge" electrode, the enzyme is highly electroactive: this allows precise manipulations of the complex redox chemistry and facilitates quantitative measurements of the interconversions between active catalytic states and the inactive oxidized form Ni(r) (also called Ni-B or "ready") as functions of pH, H(2) partial pressure, temperature, and electrode potential. Cyclic voltammograms for catalytic H(2) oxidation (current is directly related to turnover rate) are highly asymmetric (except at pH > 8 and high temperature) due to inactivation being much slower than activation. Controlled potential-step experiments show that the rate of oxidative inactivation increases at high pH but is independent of potential, whereas the rate of reductive activation increases as the potential becomes more negative. Indeed, at 45 degrees C, activation takes just a few seconds at -288 mV. The cyclic asymmetry arises because interconversion is a two-stage reaction, as expected if the reduced inactive Ni(r)-S state is an intermediate. The rate of inactivation depends on a chemical process (rearrangement and uptake of a ligand) that is independent of potential, but sensitive to pH, while activation is driven by an electron-transfer process, Ni(III) to Ni(II), that responds directly to the driving force. The potentials at which fast activation occurs under different conditions have been analyzed to yield the potential-pH dependence and the corresponding entropies and enthalpies. The reduced (active) enzyme shows a pK of 7.6; thus, when a one-electron process is assumed, reductive activation at pH < 7 involves a net uptake of one proton (or release of one hydroxide), whereas, at pH > 8, there is no net exchange of protons with solvent. Activation is favored by a large positive entropy, consistent with the release of a ligand and/or relaxation of the structure around the active site. 相似文献
16.
M. J. Folkes A. Keller J. Stejny P. L. Goggin G. V. Fraser P. J. Hendra 《Colloid and polymer science》1975,253(5):354-361
The recently observed very low-frequencyRaman bands in polyethylene open up the possibility of determining the straight-chain stem lengths within the crystal as opposed to the full periodicity constituted by crystal core plus amorphous surface layer given by lowangle X-ray diffraction. Past works (6–10) have established the correlation with lamellar thickness but leave doubts about the possibility of making the distinction just indicated. The first objective of the present work was to examine this point on crystals where the chains are inclined to different extents with respect to the lamellar surface. The samples include single-crystals grown from solution at different temperatures and oriented bulk polyethylenes. It is concluded that the low-frequencyRaman peaks correspond to the inclined chain length as opposed to the layer thickness, hence providing a measure of a chain as opposed to a platelet property. TheRaman based length figures are only slightly below those of the appropriately inclined straight traverses across the full lamellae, hence on the basis of existing understanding non-trans chain sequences are confined to a surface region which must be much narrower than required by the usually envisaged amorphous crystalline two-phase structure. Similar studies were carried out also on single crystals of the linear polyester poly(decamethylene sebacate). These demonstrate in the first place that polymers other than polyethylene can also be amenable to suchRaman studies and secondly that in this particular instance, changes in the relative thicknesses of crystal core and surface layer could be registered. The two studies in conjunction affirm the potential of the low-frequencyRaman technique for the study of polymer crystal morphology. 相似文献
17.
18.
Why carry out medicinal chemistry at a university, when it means competing with the billion-dollar research efforts of the pharmaceutical industry? In academic research, the race to get a drug to market is not the prime motivation. Instead, university-based medicinal chemistry is driven by the search for new knowledge and the opportunity to educate a new generation of chemists. Furthermore, academia can complement commercial efforts by addressing diseases neglected by private industry. 相似文献
19.
The lithiation and alkylation of three aldehydes in the form of their α-phenethylimines has been shown to yield chiral α-alkylaldehydes of 67–70% optical purity. 相似文献
20.
[reaction: see text] The enzymatic degradation of starch can be monitored electronically using single-walled carbon nanotubes (SWNTs) as semiconducting probes in field-effect transistors (FETs). Incubation of these devices in aqueous buffer solutions of amyloglucosidase (AMG) results in the removal of the starch from both the silicon surfaces and the side walls of the SWNTs in the FETs, as evidenced by direct imaging and electronic measurements. 相似文献