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81.
Bowers J Amos KE Bruce DW Webster JR 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1346-1353
The surface behavior of a range of surfactant [Ru(bipy)(2)(p,p'-dialkyl-2,2'-bipy)]Cl(2) complexes, which we express as Ru(q)(p)C(n) where n is the alkyl chain length, p refers to the substitution position on the bipyridine ligand (=4 or 5), and q (=1 or 2) is the number of substituted alkyl chains, has been examined using neutron reflectometry. The adsorption of the single-chain Ru(1)(4)C(19) and Ru(1)(5)C(19) surfactants is strongly time-dependent, taking in excess of 10 h to form an equilibrium film. It is suggested that the slow adsorption rate is related to the alkyl chain length rather than the low monomer concentration present in the solutions. At concentrations below the critical micelle concentration (cmc) of Ru(1)(4)C(19), the film of Ru(1)(5)C(19) is denser than that of Ru(1)(4)C(19) at comparable concentration, consistent with the mass densities of the bulk solids, whereas at concentrations close to and greater than this cmc the converse pertains. Close to the cmc, the adsorbed films possess an average area per molecule significantly less than the nominal headgroup area of the surfactants (approximately 30 angstroms(2) compared with approximately 100 angstroms(2)). This fact together with consideration of the thickness and density of the adsorbed films leads to the conjecture that surface aggregates may be the adsorbing units. The adsorption of the double-chain surfactant Ru(1)(p)C(19), in contrast to the behavior of the Ru(1)(p)C(19) surfactants, is weak and independent of time. This behavior is attributed to the alkyl chain orientation. The adsorption behavior of a racemic mixture of the Delta and Lambda isomers of Ru(2)(4)C(19) has been compared with that of the Delta isomer. It is found that the film of racemic material is more closely packed than that of the resolved complex. 相似文献
82.
A set of ten differential cross sections between 10 and 40 MeV for this charge exchange reaction have been analysed. In the analyses, amplitudes associated with the virtual excitation of the giant dipole and quadrupole reasonances in28Si complement those associated with the direct reaction mechanism. Such resonance effects are essential to explain the rapid energy variation of the data. 相似文献
83.
84.
Roger D. Amos 《Chemical physics letters》1980,75(3):602-612
Møller-Plesset perturbation theory is used to find the second- and third-order correlation corrections to some oneelectron properties of HC1 and CO. An estimate of the fourth-order correction is made. It is shown that the perturbed wavefunctions can be constructed efficiently using the techniques of the direct CI methods. The results are comparable in accuracy with those obtained from large-scale CI calculations, but require considerably less computation. 相似文献
85.
86.
The kinetics of biomimetic mineralization at a fatty acid monolayer interface have been measured in situ by synchrotron x-ray reflectivity. The formation of biologically relevant amorphous calcium carbonate films is affected by soluble macromolecules, supersaturation rate of change, and Mg cations. We find that these solution conditions influence mineral film formation in a complementary fashion. Poly(sodium acrylate) extends the lifetime of metastable amorphous calcium carbonate, solution saturation controls the mineral film growth rate, and Mg cations create a longer induction time. This is the first quantification of potentially competitive biomineralization mechanisms that addresses nucleation and growth of the amorphous mineral phases, which are important in biomineralization. 相似文献
87.
We evaluate the Poynting vector generated by a heavy quark moving through a thermal state of N=4 gauge theory using the gauge-string duality. A significant diffusion wake is observed as well as a Mach cone. We discuss the ratio of the energy going into sound modes to the energy coming in from the wake. 相似文献
88.
In a quest to develop an effective, scalable synthesis of (+)-spongistatin 1 ( 1), we devised a concise, third-generation scalable synthesis of (+)- 7, the requisite F-ring tetrahydropyran aldehyde, employing a proline-catalyzed cross-aldol reaction. Subsequent elaboration to (+)-EF Wittig salt (+)- 3, followed by union with advanced ABCD aldehyde (-)- 4, macrolactonization and global deprotection permitted access to >1.0 g of totally synthetic (+)-spongistatin 1 ( 1). 相似文献
89.
90.
Ley SV Abad-Somovilla A Anderson JC Ayats C Bänteli R Beckmann E Boyer A Brasca MG Brice A Broughton HB Burke BJ Cleator E Craig D Denholm AA Denton RM Durand-Reville T Gobbi LB Göbel M Gray BL Grossmann RB Gutteridge CE Hahn N Harding SL Jennens DC Jennens L Lovell PJ Lovell HJ de la Puente ML Kolb HC Koot WJ Maslen SL McCusker CF Mattes A Pape AR Pinto A Santafianos D Scott JS Smith SC Somers AQ Spilling CD Stelzer F Toogood PL Turner RM Veitch GE Wood A Zumbrunn C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(34):10683-10704
We describe in full the first synthesis of the potent insect antifeedant azadirachtin through a highly convergent approach. An O-alkylation reaction is used to unite decalin ketone and propargylic mesylate fragments, after which a Claisen rearrangement constructs the central C8-C14 bond in a stereoselective fashion. The allene which results from this sequence then enables a second critical carbon-carbon bond forming event whereby the [3.2.1] bicyclic system, present in the natural product, is generated via a 5-exo-radical cyclisation process. Finally, using knowledge gained through our early studies into the reactivity of the natural product, a series of carefully designed steps completes the synthesis of this challenging molecule. 相似文献