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排序方式: 共有354条查询结果,搜索用时 15 毫秒
41.
Wangdong Zeng Zhe Sun Tun Seng Herng Tho P. Gonalves Tullimilli Y. Gopalakrishna Kuo‐Wei Huang Jun Ding Jishan Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(30):8757-8761
The challenging synthesis of a laterally extended heptazethrene molecule, the super‐heptazethrene derivative SHZ‐CF3 , is reported. This molecule was prepared using a strategy involving a multiple selective intramolecular Friedel–Crafts alkylation followed by oxidative dehydrogenation. Compound SHZ‐CF3 exhibits an open‐shell singlet diradical ground state with a much larger diradical character compared with the heptazethrene derivatives. An intermediate dibenzo‐terrylene SHZ‐2H was also obtained during the synthesis. This study provides a new synthetic method to access large‐size quinoidal polycyclic hydrocarbons with unique physical properties. 相似文献
42.
The stoichiometry and stability constant of metal complexes with 4-(3-methoxy-salicylideneamino)-5-hydroxynaphthalene-2,7-disulfonic
acid monosodium salt (H2L) and 4-(3-methoxysalicylideneamino)-5-hydroxy-6-(2,5-dichlorophenylazo)-2,7-naphthalene disulfonic acid monosodium salt
(H2L1) were studied by potentiometric titration. The stability constants of H2L and H2L1 Schiff bases have been investigated by potentiometric titration and u.v.–vis spectroscopy in aqueous media. The dissociation
constants of the ligand and the stability constants of the metal complexes were calculated pH-metrically at 25 °C and 0.1 m KCl ionic strength. The dissociation constants for H2L were obtained as 3.007, 7.620 and 9.564 and for H2L1, 4.000, 6.525, 9.473 and 10.423, respectively. The complexes were found to have the formulae [M(L)2] for M = Co(II), Ni(II), Zn(II) and Cu(II). The stability of the complexes follows the sequence: Zn(II) < Co(II) < Cu(II)
< Ni(II). The high stability of H2L1 towards Cu(II) and Ni(II) over the other ions is remarkable, in particular over Cu(II), and may be of technological interest.
Concentration distribution diagram of various species formed in solution was evaluated for ligands and complexes. The formation
of the hydrogen bonds may cause this increased stability of ligands. The pH-metric data were used to find the stoichiometry,
deprotonation and stability constants via the SUPERQUAD computer program. 相似文献
43.
Yoon ZS Noh SB Cho DG Sessler JL Kim D 《Chemical communications (Cambridge, England)》2007,(23):2378-2380
Using the bidirectional NICS scan method in conjunction with two-photon absorption (TPA) measurements, it has proved possible to determine the relationship between pi-conjugation and aromaticity in two structurally related expanded porphyrin systems, sapphyrin and inverted sapphyrin, and establish that differences in these defining factors depend on the presence or absence of a key sp3 hybrid molecular orbital within the macrocyclic periphery. 相似文献
44.
Gui‐Xia Wang Li‐Li Shang Zhao‐Hao Li Bang‐Tun Zhao 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(7):715-717
A novel manganese coordination polymer, poly[(μ5‐thiophene‐3,4‐dicarboxylato)manganese(II)], [Mn(C6H2O4S)]n, was synthesized hydrothermally using 3,4‐thiophenedicarboxylate (3,4‐tdc2−) as the organic linker. The asymmetric unit of the complex contains an Mn2+ cation and one half of a deprotonated 3,4‐tdc2− anion, both residing on a twofold axis. Each Mn2+ centre is six‐coordinated by O atoms of bridging/chelating carboxylate groups from five 3,4‐tdc2− anions, forming a slightly distorted octahedron. The Mn2+ centres are bridged by 3,4‐tdc2− anions to give an infinite two‐dimensional layer which incorporates one‐dimensional Mn–O gridlike chains, and in which the 3,4‐tdc2− anion adopts a novel hexadentate chelating and μ5‐bridging coordination mode. The fully deprotonated 3,4‐tdc2− anion exhibits unexpected efficiency as a ligand towards the Mn2+ centres, which it coordinates through all of its carboxylate O atoms to provide the novel coordination mode. The IR spectrum of the complex is also reported. 相似文献
45.
Static adsorption of serine alkaline protease (SAP) enzyme on hydrophobic polyether sulfone (PES) ultrafiltration membranes in different ionic environments was investigated. The amount of SAP adsorbed on membranes was the lowest at its isoelectric point (IEP) where the maximum adsorption was obtained below the IEP of the enzyme. The extent of SAP adsorption in the phosphate buffer solutions including different salts followed the order: (NH4)2HPO4 > KH2PO4 > Na2HPO4-NaH2PO4 (buffer) > CaCl2 > ((NH4)2HPO4 + H2PO4 + CaCl2), which was consistent with the Hofmeister series. The zeta potentials of membranes contacted with the ionic species were calculated by streaming potential measurements and found that the increase in ionic strength decreased the electrical double layer thickness leading to a decrease in adsorption. A model based on mass balance was developed to calculate the diffusion coefficient of SAP in PES membranes. Employing experimental data evaluated in a diffusion cell along with the data of adsorption isotherms, diffusion coefficients of SAP in PES membranes in the presence of different ionic species were calculated. To detect the structural changes occurred, membrane surfaces were analysed by Fourier transform infrared-attenuated total reflectance (FTIR-ATR) measurements. 相似文献
46.
Hajjaj F Yoon ZS Yoon MC Park J Satake A Kim D Kobuke Y 《Journal of the American Chemical Society》2006,128(14):4612-4623
Porphyrin-based supramolecular macrocyclic arrays were synthesized as mimics of photosynthetic light-harvesting (LH) antennae. Pentameric and hexameric macrocyclic porphyrin arrays EP5 and EP6 were constructed by complementary coordination of m-bis(ethynylene)phenylene-linked zinc-imidazolylporphyrin Zn-EP-Zn. The proton NMR spectra of noncovalently linked N-EP5 and N-EP6 indicate fast rotation of the porphyrin moieties along the ethyne axis. These macrocycles were covalently linked and identified as C-EP5 (6832 Da) and C-EP6 (8199 Da) by mass spectrometry. Fluorescence quantum yields of C-EP2 (10.0%), C-EP5 (10.1%), and C-EP6 (11.0%), even larger than that of the unit coordination dimer C-EP1 (9.3%), were significantly increased from those of the series without the ethynylene linkage. The order of increasing fluorescence quantum yields was parallel to that of decreasing fluorescence lifetimes (C-EP1 (1.65 ns), C-EP2 (1.45 ns), C-EP5 (1.42 ns), and C-EP6 (1.38 ns)), indicating that the radiative decay rate kF increased relative to the other decay rates with an increase in the number of ring components. Based on the exciton-exciton annihilation and anisotropy depolarization times, the excitation energy hopping (EEH) times in these macrocyclic systems were obtained as 21 ps for C-EP5 and 12.8 ps for C-EP6. EEH times depend strongly on the orientation factor of the component transition dipoles in the macrocyclic arrays. The hexagonal macrocyclic array with an orientation of better transition dipole coupling resulted in faster EEH time compared to the pentagonal one. 相似文献
47.
Hwang IW Park M Ahn TK Yoon ZS Ko DM Kim D Ito F Ishibashi Y Khan SR Nagasawa Y Miyasaka H Ikeda C Takahashi R Ogawa K Satake A Kobuke Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(12):3753-3761
The excitation-energy-hopping (EEH) times within two-dimensional cyclic zinc(II)-porphyrin arrays 5 and 6, which were prepared by intermolecular coordination and ring-closing metathesis reaction of olefins, were deduced by modeling the EEH process based on the anisotropy depolarization as well as the exciton-exciton annihilation dynamics. Assuming the number of energy-hopping sites N = 5 and 6, the two different experimental observables, that is, anisotropy depolarization and exciton-excition annihilation times, consistently give the EEH times of 8.0 +/- 0.5 and 5.3 +/- 0.6 ps through the 1,3-phenylene linkages of 5 and 6, respectively. Accordingly, the self-assembled cyclic porphyrin arrays have proven to be well-defined two-dimensional models for natural light-harvesting complexes. 相似文献
48.
Ahn TK Yoon ZS Hwang IW Lim JK Rhee H Joo T Sim E Kim SK Aratani N Osuka A Kim D 《The journal of physical chemistry. B》2005,109(22):11223-11230
We have investigated the overall excitation energy relaxation dynamics in linear porphyrin arrays as well as the energy transport phenomena by attaching an energy acceptor to one end of a linear porphyrin array by using steady state and time-resolved spectroscopic measurements. We have revealed that the solvation dynamics as well as the conformational dynamics contributes significantly to the energy relaxation processes of linear porphyrin arrays. Consequently, long porphyrin arrays no longer serve as good energy transmission elements in donor-acceptor linked systems due to conformational heterogeneities which provide the non-radiative deactivation channels as energy quenchers. 相似文献
49.
Nonlinear Dynamics - The large-scale use of the Internet brings the problem of the rapid spread of computer malware over the network. Aiming at the relationship between malware, propagation paths... 相似文献
50.