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排序方式: 共有1206条查询结果,搜索用时 15 毫秒
61.
Fokin AA Tkachenko BA Gunchenko PA Gusev DV Schreiner PR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):7091-7101
The structures, strain energies, and enthalpies of formation of diamantane 1, triamantane 2, isomeric tetramantanes 3-5, T(d)-pentamantane 6, and D(3d)-hexamantane 7, and the structures of their respective radicals, cations, as well as radical cations, were computed at the B3LYP/6-31G* level of theory. For the most symmetrical hydrocarbons, the relative strain (per carbon atom) decreases from the lower to the higher diamondoids. The relative stabilities of isomeric diamondoidyl radicals vary only within small limits, while the stabilities of the diamondoidyl cations increase with cage size and depend strongly on the geometric position of the charge. Positive charge located close to the geometrical center of the molecule is stabilized by 2-5 kcal mol(-1). In contrast, diamondoid radical cations preferentially form highly delocalized structures with elongated peripheral C-H bonds. The effective spin/charge delocalization lowers the ionization potentials of diamondoids significantly (down to 176.9 kcal mol(-1) for 7). The reactivity of 1 was extensively studied experimentally. Whereas reactions with carbon-centered radicals (Hal)(3)C(*) (Hal=halogen) lead to mixtures of all possible tertiary and secondary halodiamantanes, uncharged electrophiles (dimethyldioxirane, m-chloroperbenzoic acid, and CrO(2)Cl(2)) give much higher tertiary versus secondary selectivities. Medial bridgehead substitution dominates in the reactions with strong electrophiles (Br(2), 100 % HNO(3)), whereas with strong single-electron transfer (SET) acceptors (photoexcited 1,2,4,5-tetracyanobenzene) apical C(4)-H bridgehead substitution is preferred. For diamondoids that form well-defined radical cations (such as 1 and 4-7), exceptionally high selectivities are expected upon oxidation with outer-sphere SET reagents. 相似文献
62.
The structure, vibrational spectra and electronic properties of the neutral, singly and doubly charged C52 fullerenes were studied by means of the Hartree-Fock method and density functional theory. Different isomers were considered, in particular those with the lowest possible number (five or six) of adjacent pentagons, and an isomer with a four-atom ring. For neutral and singly charged species, the most stable isomer is that with the lowest number of adjacent pentagons, namely five. However, for C(52)2+, the most stable structure has six adjacent pentagons. This finding, which contradicts the pentagon adjacency penalty rule, is a consequence of complete filling of the HOMO pi shell and the near-perfect sphericity of the most stable isomer. The simulated vibrational spectra show important differences in the positions and intensities of the vibrations for the different isomers. 相似文献
63.
Leonid M. Goldenberg Nikolai N Denisov Jan F. Biernat 《Journal of inclusion phenomena and macrocyclic chemistry》2000,38(1-4):171-186
The complexation of 13- and 16-memberedazo- and azoxycrowns with metal cations of similarionic diameter (Na+ and Ca2+; and K+,Ba2+, Ag+ and Pb2+) was studied byuv/visible spectroscopic titration in acetonitrile andMeOH. In MeOH the 13-membered azo- and azoxycrowns 1 and 2 are weakly and non-selectively bound tohard cations of similar ionic diameter, but differentcharge (Na+ and Ca2+). At the same time thebinding to the soft cation Ag+ of larger sizethan the macrocycle cavity is considerably stronger.In contrast to solutions in acetonitrile no bindingwith the small Li+ cation was found.The 16-membered azocrowns 3 and 4 alsodiscriminate silver cation in MeOH withlog K = 3.65 ± 0.1 for both compounds.Unexpectedly low bindingwith the hard barium divalent cation of similar size(log K = 1.55 ± 0.4 and 1.95 ± 0.2, respectively)was found for these compounds. Similarly to13-membered compounds no binding with the smallLi+ cation was detected. A reverse order ofselectivity was observed for these crowns inacetonitrile with binding constant for association of3 with Ba2+ (log K 5.3) considerablyhigher than for other cations. The previously observedstrong binding with the smaller Li+ and Na+cations is confirmed. 相似文献
64.
GHOLAM HOSSEIN ROUNAGHI RAZYEH SANAVI KHOSHNOOD 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(3-4):309-314
A series of competitive metal ion transport experiments have been performed. Each involved transport from an aqueous source phase across an organic membrane phase into an aqueous receiving phase. The source phase contained equimolar concentrations of cobalt(II), nickel(II), cupper(II), zinc(II), cadmium(II), silver(I) and lead(II) metal cations. The membrane phase incorporated ionophore, decyl-18-crown-6. The membrane solvents include: chloroform, dichloromethane, 1,2-dichloroethane, nitrobenzene and chloroform–nitrobenzene binary solvents. A good transport efficiency and selectivity of Pb2+ transport from aqueous solutions are observed in this investigation. The selectivity order for competitive bulk liquid membrane transport of the studied transition and post transition metal cations through chloroform is: Pb2+>Co2+>Ni2+>Ag+>Cd2+, but in the case of dichloromethane, 1,2-dichloroethane and nitrobenzene as liquid membranes, the selectivity sequences were found to be: Pb2+>Co2+>Cd2+>Cu2+>Ag+>Ni2+>Zn2+, Pb2+>Co2+>Ag+>Ni2+>Zn2+ and Pb2+>Co2+>Ni2+>Zn2+>Cd2+>Ag+, respectively. The transport rate of the metal cations in chloroform–nitrobenzene binary solvents is sensitive to the solvent composition. The transport processes were studied in absence and presence of the stearic acid and the results show that the sequence of selectivities and ion transport rates change in the presence of stearic acid. 相似文献
65.
以抑制型电导离子色谱法检测四甲基氢氧化铵溶液中痕量碱金属和碱土金属离子.色谱条件为:IonPac CS12A阳离子交换色谱柱,20mmol/L甲烷磺酸淋洗液等度淋洗,抑制型电导检测.稀释液样品通过Dionex OnGuardⅡ氢型聚苯乙烯基强酸性树脂柱和0.22μm微孔尼龙膜处理.该方法的检测限(S/N=3)在0.024μg/L~0.156μg/L之间,标准曲线在低ng/L到低μg/L范围内呈现良好线性,RSD在10%左右,回收率为88%~115%. 相似文献
66.
Brandall L. Ingle 《Journal of Coordination Chemistry》2014,67(23-24):3920-3931
Within the ATP-grasp family of enzymes, divalent alkaline earth metals are proposed to chelate terminal ATP phosphates and facilitate the formation of peptide bonds. Density functional theory methods are used to explore the impact of metal ions on peptide bond formation, providing an insight into experimental metal substitution studies. Calculations show that alkaline earth and transition metal cations coordinate with an acylphosphate reactant and aid in the separation of the phosphate leaving group. The critical biochemical reaction is proposed to proceed through the formation of a six-membered transition state in the relatively nonpolar active site of human glutathione synthetase, an ATP-grasp enzyme. While the identity of the metal ion has a moderate impact on the thermodynamics of peptide bond formation, kinetic differences are much sharper. Simulations indicate that several transition metal ions, most notably Cu2+, may be particularly advantageous for catalysis. The detailed mechanistic study serves to elucidate the vital role of coordination chemistry in the formation of peptide bonds. 相似文献
67.
68.
Muhammad Imran ul‐haq Rajesh A. Shenoi Donald E. Brooks Jayachandran N. Kizhakkedathu 《Journal of polymer science. Part A, Polymer chemistry》2013,51(12):2614-2621
Hyperbranched polyglycerols (HPGs) are globular structures with a large number of functionalizable hydroxyl groups and have excellent in vitro and in vivo biocompatibility profiles comparable to polyethylene glycol. This work introduces a facile method for the synthesis of medium molecular weights (Mws) (50–300 kDa) HPGs, which has been difficult to synthesize with low polydispersity, with the assistance of solvents by ring opening polymerization. The influence of different solvents (1,4‐dioxane, tetrahydropyran (THP), ethylene glycol diethyl ether (EGDE) and decane), solvent to glycidol ratio, concentration of glycidol and the time of polymerization on Mw and polydispersity of HPGs has been studied. The Mw and polydispersity of HPGs are significantly affected by the nature of the polymerization phase (homogeneous or heterogeneous) and chemical structure of the solvent. The differences in the solvation of the potassium cations and change in the nucleophilicity of the alkoxide anion in various solvents may be responsible for the changes in Mw and PDI of the HPG. The Mw of the HPG decreases in the order 1,4‐dioxane > THP > EGDE >decane. The microstructure, solution and thermal properties of the HPG do not depend on the nature of solvent. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2614–2621 相似文献
69.
Dr. Thies Olaf Petersen Dustin Simone Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15847-15855
Attempts to prepare previously unknown simple and very Lewis acidic [RZn]+[Al(ORF)4]? salts from ZnR2, AlR3, and HO?RF delivered the ion‐like RZn(Al(ORF)4) (R=Me, Et; RF=C(CF3)3) with a coordinated counterion, but never the ionic compound. Increasing the steric bulk in RZn+ to R=CH2CMe3, CH2SiMe3, or Cp*, thus attempting to induce ionization, failed and led only to reaction mixtures including anion decomposition. However, ionization of the ion‐like EtZn(Al(ORF)4) compound with arenes yielded the [EtZn(arene)2]+[Al(ORF)4]? salts with arene=toluene, mesitylene, or o‐difluorobenzene (o‐DFB)/toluene. In contrast to the ion‐like EtZn(η3‐C6H6)(CHB11Cl11), which co‐crystallizes with one benzene molecule, the less coordinating nature of the [Al(ORF)4]? anion allowed the ionization and preparation of the purely organometallic [EtZn(arene)2]+ cation. These stable materials have further applications as, for example, initiators of isobutene polymerization. DFT calculations to compare the Lewis acidities of the zinc cations to those of a large number of organometallic cations were performed on the basis of fluoride ion affinity. The complexation energetics of EtZn+ with arenes and THF was assessed and related to the experiments. 相似文献
70.
Mutsuo Igarashi 《Molecular Crystals and Liquid Crystals》2013,570(2):437-440
Abstract Spin-spin relaxation of 23Na-NMR is observed by the spin echo method at room temperature for Y-type zeolite loaded with Na metal without hydration. For saturated and no levels of loading, the echo decay is well fitted by single exponential function. T 2 decreases to be 0.25 times smaller by loading. This decrease of T 2 is explained semiquantitatively with assuming nuclear dipole-dipole interaction between neighboring Na. 相似文献