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91.
The syntheses of new cyano-substituted derivatives of arachno-6,8-C(2)B(7)H(13) have been achieved through the addition reactions of the arachno-6,8-C(2)B(7)H(12)(-) (1-) anion with cyano-activated olefins. The reaction of PSH+1- with tetracyanoethylene (TCNE) yielded the unusual bridging compound PSH(+)endo-6-endo-7-[micro(2)-(C(CN)(2))(2)]-arachno-6,8-C(2)B(7)H(12)(-) (PSH+2-)) resulting from cycloaddition of the TCNE at the C6-B7 edge of the anion. Consistent with its hypho skeletal electron count, an X-ray crystallographic study and DFT/GIAO calculations confirm 2(-) has a more open structure than 1-. The reaction of 1- with acrylonitrile resulted in the formation of endo-6-(NCCH(2)CH(2))-arachno-6,8-C(2)B(7)H(11)(-) (3-), which, upon acidification, afforded endo-6-(NCCH(2)CH(2))-arachno-6,8-C(2)B(7)H(12) (3) in high yield. X-ray crystallographic and DFT/GIAO studies established that the cyanoethyl fragment in 3 is substituted at the endo-position of the C6 cage-carbon. Heating 3 in THF at 50 degrees C or in toluene at 110 degrees C resulted in the quantitative isomerization of the cyanoethyl-substituent from the endo- to the exo-position at C6 to yield exo-6-(NCCH(2)CH(2))-arachno-6,8-C(2)B(7)H(12) (4). This is the first example of an endo to exo isomerization to be observed at a cage-carbon of a carborane. While heating 3 resulted in isomerization to 4, heating 3- in the presence of a small amount of 3 yielded the new ethylene-bridged 10-vertex tricarbaborane micro(6,9)-(CH(2)CH(2))-arachno-5,6,9-C(3)B(7)H(11) (5) resulting from reduction of the 3- pendant nitrile group, followed by deammination and carbon insertion. 相似文献
92.
Atoms in an ultracold highly excited sample are strongly coupled through the dipole-dipole interaction. In an effort to understand and manipulate the complicated interactions in this system we are investigating their dependence on the relative orientation of the dipoles. By focusing a 480 nm beam from a tunable dye laser into a magneto-optical trap, we produce a nearly one-dimensional sample of Rydberg atoms. The trap lies at the center of four conducting rods with which we can vary the magnitude and direction of the electric field at the trap, thus controlling the orientation of the dipoles with respect to the sample axis. We have measured the strength of the interaction for a variety of relative orientations. 相似文献
93.
Phenanthrenequinone undergoes highly efficient proton transfer processes in the presence of a thiourea-functionalised polystyrene copolymer whereas interactions with a similar benzyl-thiourea monomer show strong redox modulation of the quinone without proton transfer. 相似文献
94.
Back BB Baker MD Ballintijn M Barton DS Becker B Betts RR Bickley AA Bindel R Budzanowski A Busza W Carroll A Decowski MP García E Gburek T George N Gulbrandsen K Gushue S Halliwell C Hamblen J Harrington AS Henderson C Hofman DJ Hollis RS Hołyński R Holzman B Iordanova A Johnson E Kane JL Khan N Kulinich P Kuo CM Lee JW Lin WT Manly S Mignerey AC Noell A Nouicer R Olszewski A Pak R Park IC Pernegger H Reed C Remsberg LP Roland C Roland G Sagerer J Sarin P Sawicki P Sedykh I Skulski W Smith CE 《Physical review letters》2003,91(7):072302
We have measured transverse momentum distributions of charged hadrons produced in d+Au collisions at sqrt[s(NN)]=200 GeV. The spectra were obtained for transverse momenta 0.25
相似文献
95.
Spiteller P Bai L Shang G Carroll BJ Yu TW Floss HG 《Journal of the American Chemical Society》2003,125(47):14236-14237
The functions of six genes in the ansamitocin biosynthetic gene cluster of Actinosynnema pretiosum have been investigated by gene inactivation and chemical analysis of the mutants. They encode a halogenase (asm12), a carbamoyltransferase (asm21), a 20-O-methyltransferase (asm7), a 3-O-acyltransferase (asm19), an epoxidase (asm11), and an N-methyltransferase (asm10), respectively, and are responsible for the six post-PKS modification steps in ansamitocin formation. Several of the enzymes have relaxed substrate specificities, resulting in multiple parallel pathways in a metabolic grid, albeit with a preferred sequence of reactions as listed above. 相似文献
96.
[reaction: see text] Mellitic triimides undergo three sequential one-electron reduction processes whose potentials are significantly lowered in the presence of alkyl thioureas. The two sequential reductions of benzene diimides are similarly stabilized. Calculation of the relative free energy change between the different electronic states of the imide acceptors and their corresponding alkyl thiourea complexes indicates dramatic increases in hydrogen bond strength with increasing acceptor charge density. 相似文献
97.
98.
We have investigated the implantation of Ag(N) (N = 20-200) clusters into a graphite substrate over the range of energies (E) 0.75-6 keV using molecular dynamics simulations. We find that after implantation the silver clusters remain coherent, albeit amorphous, and rest at the bottom of an open tunnel in the graphite created by the impact. It is found that the implantation depth of the clusters varies linearly as E/N2/3. We conclude that the cluster is decelerated by a constant force proportional to its cross-sectional area. We also identify a threshold energy for surface penetration associated with elastic compression of the graphite substrate. 相似文献
99.
We describe two experiments in which we investigate the synchronization of coupled periodic oscillators. Each experimental system consists of two identical coupled electronic periodic oscillators that display bursts of desynchronization events similar to those observed previously in coupled chaotic systems. We measure the degree of synchronization as a function of coupling strength. In the first experiment, high-quality synchronization is achieved for all coupling strengths above a critical value. In the second experiment, no high-quality synchronization is observed. We compare our results to the predictions of the several proposed criteria for synchronization. We find that none of the criteria accurately predict the range of coupling strengths over which high-quality synchronization is observed. (c) 2000 American Institute of Physics. 相似文献
100.
Sakari Leino Patrick JC May Paavo Alku Lassi A Liikkanen Hannu Tiitinen 《BMC neuroscience》2007,8(1):78