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The method is applied to six compounds each containing a three-membered ring. It is found that a cyclopropane ring interacts with ether oxygen attached to it to give some of the features of a -electron system. Inclusion of N or O in the three-membered ring lowers the top filled and bottom vacant levels, especially the latter.  相似文献   
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The reaction of norbornene with lead tetraacetate is found to be much more complex than previously reported. In acetic acid and in benzene, the syn-7-norbornenyl, 3-nortricyclyl, and syn and anti-7-acetoxy-exo-2-norbornyl acetates were characterized. In methanol, the isolated products represented most of those expected from the competition of methanol and acetate in the neutralization of the intermediate carbocations. The reaction of norbornene with thallium trinitrate in the above solvents yielded very complex mixtures besides the above mentioned products which were formed in about 50% yield.  相似文献   
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A classical density functional formalism has been developed to predict the position-orientation number density of structured fluids. It is applied to the liquid-vapor interface of pure water, where it consists of a classical term, a gradient correction, and an anisotropic term that yields order through density gradients. The model is calibrated to predict that water molecules have their dipole moments almost parallel to a planar interface, while the molecular plane is parallel to it on the liquid side and perpendicular to it on the vapor side. For a planar interface, the surface tension obtained is twice its experimental value, while the surface potential is in qualitative agreement with that calculated by others. The model is also used to predict the orientation of water molecules near the surface of droplets, as well as the dependence of equilibrium vapor pressure around them on their size.  相似文献   
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The influence of the number of 3, 3, 3-trifluoropropyl(methyl)siloxane links (Φ/Φ) in the cyclotetrasiloxanes ΦmD4-m, where D represents the dimethylsiloxane link and m=0–4, on the rearrangement of these compounds in acetone solution under the action of sodium siloxanolate has been studied. The rearrangement takes place with the formation of a linear polysiloxane the degradation of which yields, in addition to the initial ring, cyclosiloxanes with a different structure. The rate of rearrangement of ΦmD4-m and of the formation of a linear polysiloxane rises with an increase in m from 0 to 3. The equilibrium concentration of the linear polysiloxane formed from ΦmD4-m is inversely proportional to m. Results have been obtained on the kinetics of the formation of the cyclosiloxanes ΦmDn, where m=0–5, n=0–5, and m+n=3–6, in the rearrangement of the rings ΦD3, Φ2D2, Φ3D, and Φ4. The reactivity of the siloxane links rises in the sequence ~ (CH3)2Si-O-Si(CH3)2 ~<~ (CF3CH2CH2)-(CH3) Si-O-Si(CH3)2 ~<(CF3CH2CH2) (CH3)Si-O-Si(CH3) (CH2CH2CF3) ~. Because of the negative inductive effect transferred through the siloxane links, the 3, 3, 3-trifluoropropyl groups strongly activate the siloxane ring with respect to nucleophiiic reagents.  相似文献   
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The unique binding event between Escherichia coli single-stranded DNA binding protein (SSB) and single-stranded oligonucleotides conjugated to gold (Au) nanoparticles is utilized for the electrochemical detection of DNA hybridization. SSB was attached onto a self-assembled monolayer (SAM) of single-stranded oligonucleotide modified Au nanoparticle, and the resulting Au-tagged SSB was used as the hybridization label. Changes in the Au oxidation signal was monitored upon binding of Au tagged SSB to probe and hybrid on the electrode surface. The amplified oxidation signal of Au nanoparticles provided a detection limit of 2.17 pM target DNA, which can be applied to genetic diagnosis applications. This work presented here has important implications with regard to combining a biological binding event between a protein and DNA with a solid transducer and metal nanoparticles.  相似文献   
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