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941.
942.
Ju Wang Zuo Yin Yang Xiu Li Wang Jing Chang Zhang Wei Liang Cao State Key Laboratory of Chemical Resource Engineering Faculty of Science Beijing University of Chemical Technology Beijing China 《中国化学快报》2007,18(2):244-246
The conformational conversion of 1,3-dioxane guest encapsulated inside a cylindrical capsular host was investigated with PM3 method and single point energies were evaluated by B3LYP method. When entrapped in the capsule, the guest tumbles were slower than that in the free condition. The influences of the inner phase of the capsule on the guest conformational conversion were discussed in detail. 相似文献
943.
The 1205 classical isomers of fullerene C58, as well as one quasi-fullerene C58 isomer with a heptagonal ring (labeled as Cs:hept) have been investigated by the quantum chemical methods PM3, HCTH/3-21G, and B3LYP/6-31G(d). Isomer C3v:0001, which has the lowest number of adjacent pentagons, is predicted to be the most stable isomer, but the quasi-fullerene isomer Cs:hept is only 2.50 kcal mol-1 higher in energy. Systematic investigations of the electronic properties of C3v:0001 and Cs:hept find that the C3v:0001 isomer has high vertical electron affinity (3.19 eV). The nucleus-independent chemical shifts (NICS) value at the center of Cs:hept (-5.1 ppm) is more negative than that of C60 (-2.8 ppm). The NICS value at the center of the heptagonal ring in Cs:hept (-2.5 ppm) indicates weakly aromatic character. In contrast, the C58(6-) and C58(8-) ions of the C3v:0001 and Cs:hept geometries possess large aromatic character, with NICS values between -14.0 and -26.2 ppm. To clarify the thermodynamic stabilities of C58 isomers at different temperatures, the entropy contributions are taken into account on the basis of the Gibbs energy at the B3LYP/6-31G(d) level. The C3v:0001 isomer prevails in a wide range of temperatures, and the Cs:hept isomer is also an important component around 2800 K. The IR spectra of C58 isomers are simulated to facilitate experimental identification of different isomers. In addition, the electronic spectra and the second-order hyperpolarizabilities are predicted by ZINDO and the sum-over-states model. The static second-order hyperpolarizability of the C3v:0001 isomer is 96.5 % larger than that of C60, and its second-order hyperpolarizabilities at external field frequencies are at least nine times larger than those of C60. 相似文献
944.
945.
贫水电解质体系制备多孔阳极氧化铝模板的研究 总被引:3,自引:0,他引:3
在有机溶剂为主的含草酸电解质中,研究了大孔径有序度高的阳极氧化铝(AAO)的一步法电化学制备.实验证实,电解质中水含量的降低能够有效抑制铝的电氧化速率和溶解速率,使得其氧化膜孔道的生长能够稳定进行,所得到的六方孔道排列有序度明显高于纯水溶剂制备的电解质体系下的产物.考察了水含量、有机溶剂种类以及电解质浓度对AAO模板孔道形貌的影响.结果表明,有机溶剂贫水电解质体系使得电氧化电压的选取范围比水溶液电解质体系更宽,孔径连续可调,反应条件温和.该方法适合于制备均匀大孔径的AAO模板. 相似文献
946.
Inrecentyears,thenewsedricrystallinepolymersyndiotacticp0lystyrene(sPS)hasat-ITactedmuchattentionduetoitsg0odchendcalresistanceandenhancedmechanicalperformanceatelevatedtemPeratUre.'H0wever,itexhibitshighbrittlenessandpoorimPact-resistanceandtCar-resistance.2Therefore,itisnecessarytomodifyitwithtougheningpolyIners.AsimPlemeth0dto0verc0methedriscibilityofatwo-phaseblendofsPSandatougheningpolymristotwrovetheinterfacialaffmity,wheretheadditionofablockcoP0lymerisconsideredtobemosteffective.3… 相似文献
947.
We have investigated the electrochemical genosensing properties of gold nanoparticle–carbon nanotube hybrid. Thiolated oligonucleotide probes and mercaptohexanol were self-assembled onto the Au–CNT hybrid. The hybridization events of target oligonucleotides are monitored using electrochemical impedance spectroscopy, cyclic voltammetry and a.c. voltammetry techniques. A redox-active mediator is used to detect the oxidation of guanine residues. The as-fabricated genosensor is able to differentiate between complementary and mismatched hybridizations, relying on the oxidation current of the guanine residues mediated via . 相似文献
948.
Ye S Zhou W Abe M Nishida T Cui L Uosaki K Osawa M Sasaki Y 《Journal of the American Chemical Society》2004,126(24):7434-7435
A highly selective ligand exchange reaction is realized in the self-assembled monolayer (SAM) of a triruthenium cluster on a gold electrode surface under precise electrochemical potential control. CO as well as NO molecules, which are known to play key roles in many chemical, biological, and environmental systems, can be efficiently introduced into the SAM by electrochemically tuning the electronic state of the Ru site. These unique surface reactions are more convenient and efficient than conventional ligand exchange reactions in solution and could be used for the elucidation of the electron-transfer mechanism in a biological system as well as in the development of molecular sensors and devices. 相似文献
949.
水热合成CdS纳米晶体的形貌控制研究 总被引:4,自引:0,他引:4
研究了水热合成CdS纳米晶体形貌的化学控制,选择不同的络合试剂为模板,研究其对水热合成CdS纳米晶体形貌的影响.实验发现若以络合试剂乙二胺、甲胺为模板时,产品CdS晶体的形貌分别为(20~30) nm×(200~600) nm和(40~50) nm×(200~600) nm尺寸的纳米棒;而以络合试剂吡啶、 氨为模板时,产品CdS晶体的形貌分别为平均尺寸约30 nm和20 nm的纳米颗粒.用XRD、TEM、XPS、PL和Raman光谱等技术对所得CdS纳米棒进行了表征.同时对水热合成CdS纳米晶体形貌的模板控制机制进行了探讨,提出了一种水热合成CdS纳米棒的络合物结构诱导生长机理. 相似文献
950.
Facile synthesis of 6(E)-geranylgeraniol-19-oic acid 1,a naturally occurring alicyclic diterpene acid, by a Horner-Wadsworth-Emmons olefination of two readily available fragments 2 and 3,is described. 相似文献