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971.
972.
The self‐complementary tetrameric propargyl triols 8, 14, 18 , and 21 were synthesized to investigate the duplex formation of self‐complementary, ethynylene‐linked UUAA, AAUU, UAUA, and AUAU analogues with integrated bases and backbone (ONIBs). The linear synthesis is based on repetitive Sonogashira couplings and C‐desilylations (34–72% yield), starting from the monomeric propargyl alcohols 9 and 15 and the iodinated nucleosides 3, 7, 11 , and 13 . Strongly persistent intramolecular H‐bonds from the propargylic OH groups to N(3) of the adenosine units prevent the gg‐type orientation of the ethynyl groups at C(5′). As such, an orientation is required for the formation of cyclic duplexes, this H‐bond prevents the formation of duplexes connected by all four base pairs. However, the central units of the UAUA and AAUU analogues 18 and 14 associate in CDCl3/(D6)DMSO 10 : 1 to form a cyclic duplex characterized by reverse Hoogsteen base pairing. The UUAA tetramer 8 forms a cyclic UU homoduplex, while the AUAU tetramer 21 forms only linear associates. Duplex formation of the O‐silylated UUAA and AAUU tetramers is no longer prevented. The self‐complementary UUAA tetramer 22 forms Watson–Crick‐ and Hoogsteen‐type base‐paired cyclic duplexes more readily than the sequence‐isomeric AAUU tetramer 23 , further illustrating the sequence selectivity of duplex formation. 相似文献
973.
I. S. Belostotskaya V. B. Vol'eva N. L. Komissarova M. O. Dekaprilevich V. N. Khrustalev A. Yu. Karmilov V. V. Ershov 《Russian Chemical Bulletin》1997,46(7):1272-1280
Oxidative transformations of 2-dialkylaminomethyl-4,6-di-tert-butylphenols depend on the nature of the oxidant, the character of the substituents at the nitrogen atom, and the medium.
A mechanism of the oxidation of these compounds is suggested. The molecular structure of the compound obtained as a result
of oxidative trimerization of 2-dimethylaminomethyl-4,6-di-tert-butylphenol was established by X-ray structural analysis.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1328–1335, July, 1997. 相似文献
974.
Zein films plasticized with oleic acid were formed by solution casting, by the stretching of moldable resins, and by blown film extrusion. The effects of the forming process on film structure were investigated by X-ray diffraction. Wide-angle X-ray scattering (WAXS) patterns showed d-spacings at 4.5 and 10 A, which were attributed to the zein alpha-helix backbone and inter-helix packing, respectively. The 4.5 A d-spacing remained stable under processing while the 10 A d-spacing varied with processing treatment. Small-angle X-ray scattering (SAXS) detected a long-range periodicity for the formed films but not for unprocessed zein, which suggests that the forming process-promoted film structure development is possibly aided by oleic acid. The SAXS d-spacing varied among the samples (130-238 A) according to zein origin and film-forming method. X-ray scattering data suggest that the zein molecular structure resists processing but the zein supramolecular arrangements in the formed films are dependent on processing methods. Structural model for a zein molecular aggregate (based on Matsushima et al.10). Rectangular prisms of individual zein molecules are hexagonally aligned parallel to each other. 相似文献
975.
Cl···O intramolecular contacts are analysed here. Hence the Cambridge Structural Database (CSD) search was performed to find
five-membered Cl–C=C–C=O pseudo-rings closed through Cl···O intramolecular contacts. Such rings were analysed and it was found
that some of Cl···O distances are smaller than the corresponding sum of van der Waals radii. Additionally ab initio MP2/6-311++G(d,p)
calculations and AIM analyses were carried out here on 3-chloropropenal and its fluoro derivatives to deepen the nature of
intramolecular Cl···O interactions, some of findings may indicate that they are attractive and stabilizing ones.
This paper is dedicated to Prof. T. M. Krygowski on the occasion of his 70th birthday 相似文献
976.
The adsorption, diffusion and desorption of chlorine on and from stoichiometric, reduced and partially reduced (defective) rutile TiO2{110} are investigated using ab initio density functional theory (DFT) calculations. Theoretical results are compared with experimental investigations, and microkinetic simulations based on DFT values are then used to verify the diffusion mechanisms assumed in the experimental investigations. 相似文献
977.
用杂化密度泛函B3LYP方法研究了(AB)8(AB=BN,AlP,GaAs,InSb)团簇环形结构的平衡几何构型、电子结构、振动特性以及极化率。计算结果表明,(AB)8团簇的双层环状结构中,每个A(B)原子都与3个B(A)原子成键,且Ⅴ族元素的原子比Ⅲ族元素的原子更接近团簇中心,(BN)8、(AlP)8、(GaAs)8、(InSb)8的平均极化率依次增大,IR和Raman谱峰发生红移。另外,讨论了热力学稳定性和动力学稳定性的变化。 相似文献
978.
喷雾热解法合成球形(Y,Gd)BO3:Eu荧光粉的研究 总被引:1,自引:0,他引:1
采用喷雾热解法合成了无团聚的球形(Y,Gd)BO3∶Eu荧光粉。研究了各因素对(Y,Gd)BO3∶Eu荧光粉体的结晶性能、外观形貌及发光强度的影响。结果表明,按120%硼酸的化学计量比于900℃喷雾热解,再经过1200℃后处理2 h,可以合成结晶良好的(Y,Gd)BO3∶Eu荧光粉体;喷雾热解溶液的浓度和载气流量对荧光粉的外观形貌影响较大;铕含量为10%时可以获得最佳的发光强度。在优化喷雾热解实验条件下成功合成出良好发光强度的PDP用(Y0.6Gd0.3)BO3∶Eu0.1荧光粉。 相似文献
979.
980.
Densities of four aqueous NaNO3 solutions (0.100, 0.303, 0.580, 0.892 mol-kg–1 H2O) have been measured in the liquid phase with a constant-volume piezometer immersed in a precision liquid thermostat. Measurements were made at ten isotherms between 292 and 573 K. The range of pressure was 0.1–30 MPa. The total uncertainty of density, pressure, temperature, and concentration measurements were estimated to be less than 0.06%, 0.05%, 10 mK, and 0.014%, respectively. Values of saturated densities were determined by extrapolating experimental P- data to the vapor pressure at fixed temperature and composition. Apparent molar volumes were derived using measured values of density for the solutions and for pure water. The apparent molar volumes were extrapolated to zero concentration to yield partial molar volumes at infinite dilution. The temperature, pressure, and concentration dependence of partial and apparent molar volumes were studied. The measured values of density and apparent and partial molar volume were compared with data reported in the literature. 相似文献