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161.
162.
Peter Wallimann Sebastiano Mattei Paul Seiler Franois Diederich 《Helvetica chimica acta》1997,80(8):2368-2390
Cyclophanes 3 and 4 were prepared as initiator cores for the construction of dendrophanes (dendritic cydophanes) 1 and 2 , respectively, which mimic recognition sites buried in globular proteins. The tetra-oxy[6.1.6.1]paracyclophane 3 was prepared by a short three-step route (Scheme 1) and possesses a cavity binding site shaped by two diphenylmethane units suitable for the inclusion of flat aromatic substrates such as benzene and naphthalene derivatives as was shown by 1H-NMR binding titrations in basic D2O phosphate buffer (Table 1). The larger cyclophane 4 , shaped by two wider naphthyl(phenyl)methane spacers, was prepared in a longer, ten-step synthesis (Scheme 2) which included as a key intermediate the tetrabromocyclophane 5 . 1H-NMR Binding studies in basic borate buffer in D2O/CD3OD demonstrated that 4 is an efficient steroid receptor. In a series of steroids (Table 1), complexation strength decreased with increasing substrate polarity and increasing number of polar substituents; in addition, electrostatic repulsion between carboxylate residues of host and guest also affected the binding affinity strongly. The conformationally flexible tetrabromocyclophane 5 displayed a pronounced tendency to form solid-state inclusion compounds of defined stoichiometry, which were analyzed by X-ray crystallography (Fig. 2). 1,2-Dichloroethane formed a cavity inclusion complex 5a with 1:1 stoichiometry, while in the 1:3 inclusion compound 5b with benzene, one guest is fully buried in the macrocyclic cavity and two others are positioned in channels between the Cyclophanes in the crystal lattice. In the 1:2 inclusion compound 5c , two toluene molecules penetrate with their aromatic rings the macrocyclic cavity from opposite sides in an antiparallel fashion. On the other hand, p-xylene (= 1,4-dimethylbenzene) in the 1:1 compound 5d is sandwiched between the cyclophane molecules with its two Me groups penetrating the cavities of the two macrocycles. In the 1:2 inclusion compound 5e with tetralin (= 1,2,3,4-tetrahydronaphthalene), both host and guest are statically disordered. The shape of the macrocycle in 5a – e depends strongly on the nature of the guest (Fig. 4). Characteristic for these compounds is the pronounced tendency of 5 to undergo regular stacking and to form channels for guest inclusion; these channels can infinitely extend across the macrocyclic cavities (Fig. 6) or in the crystal lattice between neighboring cyclophane stacks (Fig. 5). Also, the crystal lattice of 5c displays a remarkable zig-zag pattern of short Br…?O contacts between neighboring macrocycles (Fig. 7). 相似文献
163.
164.
165.
Let {ø n (dμ)} be a system of orthonormal polynomials on the unit circle with respect to a measuredμ. Szegö's theory is concerned with the asymptotic behavior ofø n (dμ) when logμ′∈L 1. In what follows we will discuss the asymptotic behavior of the ratioø n (dμ 2)/ø n (dμ 1) on the unit circle whendμ 1 anddμ 2 are close in a sense (e.g.,dμ 2=gdμ 1, where g≥0 is such thatQ(e it )g(t) andQ(e it )/g(t) are bounded for a suitable polynomialQ) and μ 1 ′ >0 almost everywhere or (a somewhat weaker requirement) lim n→∞Φ n (dμ 1,0)=0 for the monic polynomial Φ n . The asymptotic behavior of the same fraction outside the unit circle was discussed in an earlier paper. 相似文献
166.
167.
Junliang Tian Chen-Lin Chou W. D. Ehmann 《Journal of Radioanalytical and Nuclear Chemistry》1987,110(1):261-274
Instrumental neutron activation analysis was used for the determination of 31 major and trace elements in 32 samples from the Xinji Loess Section, Shaanxi Province, China. Interferences, including those from uranium fission products, were evaluated and corrections applied where necessary. The 39.7-meter deep section comprises of Lishi Loess of the middle Pleistocene (Q2) and Malan Loess of the late Pleistocene (Q3). The section is characterized by the presence of 5 layers of paleosol, and each paleosol is underlain by a precipitation layer. When the elemental abundances are converted to a carbonate-free basis, there is little compositional difference among the carbonate-free fractions of loess, paleosol and precipitation layers. This indicates that dissolution of carbonate minerals by downward-moving surface water was an important process in paleosol formation while other minerals were not severely weathered and elemental fractionation was minimal. The parent materials of the paleosol and precipitation layers closely resemble the loess layers in their elemental abundances, which suggests that all layers in the section have a compositionally similar source. 相似文献
168.
Paul I. Surjasasmita Ben S. Freiser 《Journal of the American Society for Mass Spectrometry》1993,4(2):135-144
In this paper we report an extension of our earlier study on the structure of Alfacetone)2 + Collision-induced dissociation (CID) on MfacetoneXacetone-d6)+ for M = Al, Fe, Co, and Cu yields primarily, if not exclusively, nearly equal amounts of acetone and acetone-d6. Likewise, infrared multiphoton dissociation (IRMPD) at 10.6 μm yields, exclusively, nearly equal losses of the labeled and unlabeled acetones. These results suggest that the two acetone ligands bind in an equivalent fashion. Sc+ was also studied, which proved to be the most interesting. Sc+ reacts with acetone to form primarily ScO+, which undergoes higher order reactions leading to several products including ScO(acetone)2 +. IRMPD on this ion produces ScO(acetone-d6)(CD2CO)+, while its perdeuterated analog also produces ScO(acetone-d6)+ in addition to ScO(acetone-d6(CD2CO)+. The IRMPD results are supplemented by studying the primary and higher order reactions of Sc+ with acetone, as well as the CID of ScO(acetone)2 +. Finally, a qualitative assessment of the infrared photodissociation cross sections is given. It is found that the relative photodissociation cross sections follow the orders Co(acetone-d6)2 + > Co(acetone)(acetone-d6) > Co(acetone)2 + and Co(acetone-d6)+ > Co(acetone)+. 相似文献
169.
Svilen Bobev Paul H. Tobash Joe D. Thompson John L. Sarrao 《Journal of solid state chemistry》2005,178(6):2091-2103
A number of rare-earth alumo-silicides (R-Al-Si) have been synthesized from the corresponding elements by high-temperature reactions, carried out in excess of aluminum to serve as a flux. Under these experimental conditions, large single crystals of all R-Al-Si ternary phases were readily produced. The crystal structures these ternaries adopt were studied by means of powder and single-crystal X-ray diffraction and were classified as follows: (1) the early rare-earths (R=La, Ce, Pr, Nd, Sm, Gd) yield RAlxSi2−x, x∼1, non-stoichiometric ternary derivatives of the body-centered α-ThSi2-type; (2) the late rare-earths (R=Tb, Dy, Ho, Er, Tm) form stoichiometric R2Al3Si2 compounds that crystallize in the C-centered monoclinic Y2Al3Si2-type; (3) the divalent Eu and Yb produce EuAl2Si2 and YbAl2Si2 with the trigonal CaAl2Si2-type, whereas the last lanthanide element, Lu, forms LuAlSi with C-centered orthorhombic YAlGe-type. These structural trends are reviewed, and the evolution of the basic physical properties such as magnetism, heat capacity and electrical resistivity when moving across the series is described in detail. 相似文献
170.
Roy Edward Bruns Paul Martin Kuznesof James Elton Moore 《Journal of Molecular Structure》1975,29(2):211-223
CNDO molecular orbital calculations have been performed to analyze donor—acceptor interactions between molecular chlorine and benzene, toluene, mesitylene and hexamethylbenzene and the, as yet, unreported chlorine—hexafluorobenzene and carbon disulfide—benzene pairs. The stabilization energy and the dipole moment and its derivative (?p/?RCICI) calculated for the benzene—chlorine complex are in good agreement with the estimated experimental values. The trends in the experimental stabilization energies and the Cl-Cl vibrational frequencies with increasing methyl substitution appear to be well reproduced by the calculations. The charge transferred from the benzene donor is polarized toward the outer chlorine atom or sulfur atom. For hexafluorobenzene-chlorine the direction of electronic charge polarization is reversed from that of the benzene and methylbenzene complexes. The calculated results are discussed within the framework of Muliiken's simplified resonance theory for complexes. 相似文献