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991.
Aratani N Cho HS Ahn TK Cho S Kim D Sumi H Osuka A 《Journal of the American Chemical Society》2003,125(32):9668-9681
Electronically coupled porphyrin arrays are suitable for artificial light harvesting antenna in light of a large absorption cross-section and fast excitation energy transfer (EET). Along this line, an artificial energy transfer model system has been synthesized, comprising of an energy donating meso-meso linked Zn(II) porphyrin array and an energy accepting 5,15-bisphenylethynylated Zn(II) porphyrin linked via a 1,4-phenylene spacer. This includes an increasing number of porphyrins in the meso-meso linked Zn(II) porphyrin array, 1, 2, 3, 6, 12, and 24 (Z1A, Z2A, Z3A, Z6A, Z12A, and Z24A). The intramolecular singlet-singlet EET processes have been examined by means of the steady-state and time-resolved spectroscopic techniques. The steady-state fluorescence comes only from the acceptor moiety in Z1A-Z12A, indicating nearly the quantitative EET. In Z24A that has a molecular length of ca. 217 A, the fluorescence comes largely from the acceptor moiety but partly from the long donor array, indicating that the intramolecular EET is not quantitative. The transient absorption spectroscopy has provided the EET rates in real time scale: (2.5 ps)(-1) for Z1A, (3.3 ps)(-1) for Z2A, (5.5 ps)(-1) for Z3A, (21 ps)(-1) for Z6A, (63 ps)(-1) for Z12A, and (108 ps)(-1) for Z24A. These results have been well explained by a revised F?rster equation (Sumi formula), which takes into account an exciton extending coherently over several porphyrin pigments in the donor array, whose length is not much shorter than the average donor-acceptor distance. Advantages of such strongly coupled porphyrin arrays in light harvesting and transmission are emphasized in terms of fast EET and a large absorption cross-section for incident light. 相似文献
992.
Dai JC Wu XT Fu ZY Cui CP Hu SM Du WX Wu LM Zhang HH Sun RQ 《Inorganic chemistry》2002,41(6):1391-1396
Three novel complexes, Cd3tma2*13H2O (1), Cd3tma2*dabco*2H2O (2), and Cd3Htma3*8H2O (3) (tma = trimesate), of cadmium(II)-trimesate coordination polymers are obtained from hydrothermal reaction. 1 (C18H32O25Cd3) crystallizes in the monoclinic C2/c space group [a = 18.985(2) A, b = 7.3872(6) A, c = 20.432(2) A, = 97.1660(10), and Z = 4]. 2 (C24H22N2O14Cd3) crystallizes in the monoclinic P2(1)/c space group [a = 10.1323(2) A, b = 19.5669(5) A, c = 13.15880(10) A, = 108.9810(10), and Z = 4]. 3 (C27H28O26Cd3) belongs to the trigonal P31c space group [a = 15.7547(3) A, b = 15.7547(3) A, c = 7.93160(10) A, and Z = 2]. The Cd(II) centers in the three complexes are bridged by tma ligands in the coordination fashion of unidentate, bridging unidentate, bidentate, chelating bis-bidentate, chelating/bridging bis-bidentate, or chelating/bridging bidentate to form the T-shaped molecular bilayer motif for 1, chicken-wire-like motif for 2, and honeycomb-like porous structure for 3, respectively, in which the T-shaped molecular bilayer motif and chicken-wire-like motif are further interlinked in interdigitating or alternating fashion to construct the different coordination architectures. These three complexes exhibit strong fluorescent emission bands at 355 nm (lambda(ex) = 220 nm) for 1, 437 nm (lambda(ex) = 365 nm) for 2, and 353 nm (lambda(ex) = 218 nm) for 3 in the solid state at room temperature. 相似文献
993.
A novel one-dimensional complex [Zn(NIT4py)2(DTB)2(H2O)2] (1), with mixed ligands [where NIT4py is 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and DTB is 3,5-dinitrobenzoate] has been synthesized and characterized by elemental analyses, i.r., u.v.–vis spectra, thermogravimetric analysis, X-ray single crystal diffraction and magnetic measurements. The complex crystallizes in the triclinic crystal system and space group Pî. The Zn II ion is in a distorted octahedral environment: two nitrogen atoms from two NIT4py entities, two oxygen atoms from two DTB units in the basal plane; and two oxygen atoms from the two water molecules in the axial position. The [Zn(NIT4py)2(DTB)2(H2O)2] units are connected as a one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the two radicals. 相似文献
994.
The aggregation behavior of fluorinated surfactant in aqueous solution was investigated using dissipative particle dynamics (DPD) simulation method. Simulation results show that fluorinated surfactants behave mainly as their hydrocarbon analogues, having similar sequences of phases and aggregate structures, which are capable of building micelle, hexagonal phase and lamellar phase. But fluorinated surfactants also show interesting differences from hydrocarbon analogues, which can easily form hexagonal and lamellar structures with comparative little curvature. They can also form ellipsoid or rod-like micelles even in very low concentrations instead of spheroid ones. The dynamic aggregation behavior of fluorinated surfactants, as well as the comparison with hydrogenated ones, was also investigated. 相似文献
995.
氯化聚乙烯弹性体的固相法合成 总被引:2,自引:0,他引:2
讨论了以固相法合成氯化聚乙烯(CPE)弹性体的过程.实验结果表明,以固相氯化反应所得的CPE,其大分子链上Cl取代基的分布比水相悬浮法更均匀.氯化过程的温度直接影响氯化速度及分子结构,如残留结晶、氯分布等.而聚乙烯颗粒表面与内部的氯化程度取决于氯化速度.大分子链上Cl取代基对邻近基团的氯化起阻碍作用 相似文献
996.
Masaoki Oku Toetsu Shishido Takeshi Shinohara Qiang Sun Yoshiyuki Kawazoe Kazuo Nakajima Kazuaki Wagatsuma 《Journal of solid state chemistry》2004,177(2):457-460
The solid solutions of ScBRh3-ScRh3 and CeBRh3-CeRh3 are synthesized by the arc melting method, where RBRh3 and RRh3 (R=rare earth element) have perovskite and AuCu3 type structures, respectively. The binding energy of Sc 2p3/2 for ScBxRh3 increases with the boron concentration. The Knight shift of 45Sc observed by nuclear magnetic resonance spectroscopy decreases with increase of boron concentration. The decrement of the Knight shift corresponds the Sc 4s electron density at the Fermi level. The intensity ratio of f2: f1: f0 of Ce 3d XPS spectrum changes with boron concentration of CeBxRh3. It is concluded that in both cases of ScBxRh3 and CeBxRh3 the charge on the atoms on A-site changes with the concentration of the atoms on B-site, where the atoms are not directly bound. 相似文献
997.
Dongping Wang Mei Wang Xiuna Wang Rong Zhang Jia Ma Licheng Sun 《Journal of molecular catalysis. A, Chemical》2007,270(1-2):278-283
Chiral (pyrrolidine salen)Mn(III) complexes 1 with an N-benzoyl group and 2 with an N-isonicotinoyl group as well as the corresponding N-methyl (3) and N-benzyl (4) pyridinium salts of 2 were synthesized. The catalytic properties of 1–4 and 2 with excess CH3I were explored to figure out the influence of the internal pyridinium salt in the catalyst on asymmetric epoxidation of substituted chromenes with NaClO/PPNO as an oxidant system in the aqueous/organic biphasic medium. The (pyrrolidine salen)Mn(III) complexes with an internal pyridinium salt, either formed in situ or isolated, displayed higher activities than analogous complexes 1, 2 and Jacobsen's catalyst in the aforementioned reaction, with comparable high yields and ee values. The acceleration of the reaction rate is attributed to the phase transfer capability of the built-in pyridinium salt of the (salen)Mn(III) catalyst. The effect of the internal pyridinium salt on the epoxidation of substituted chromenes is similar to that of the external pyridinium salts and ammonium halides. 相似文献
998.
A new compound (5R, 10R)-3,8-dihydroxy-5,10-diethoxy-5,10-dihydrochromeno[5,4,3-cde]chromene monohydrate was obtained from 3,4-dihydroxybenzaldehyde in aerobic basic aqueous ethanol solution in the presence
of manganese chloride and triethylamine and crystallized in orthorhombic P212121 space group (denoted as 1). When 1 was recrystallized from aqueous methanol, it was transformed to another crystal (2) with the same composition but in P21/n space group. The drastic difference in the extensive hydrogen bond network makes 1 a 3D and 2 a 2D infinite supramolecular structure, respectively. 相似文献
999.
Low-temperature heat capacities of the compound Na(C4H7O5)·H2O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are ΔtransHm = (5.75 ± 0.01) kJ mol−1 and ΔtransSm = (18.47 ± 0.02) J K−1 mol−1. The enthalpy and entropy of the dehydration are ΔdHm = (15.35 ± 0.03) kJ mol−1 and ΔdSm = (41.35 ± 0.08) J K−1 mol−1. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations. 相似文献
1000.
Geney R Sun L Pera P Bernacki RJ Xia S Horwitz SB Simmerling CL Ojima I 《Chemistry & biology》2005,12(3):339-348
A new computational docking protocol has been developed and used in combination with conformational information inferred from REDOR-NMR experiments on microtubule bound 2-(p-fluorobenzoyl)paclitaxel to delineate a unique tubulin binding structure of paclitaxel. A conformationally constrained macrocyclic taxoid bearing a linker between the C-14 and C-3'N positions has been designed and synthesized to enforce this "REDOR-taxol" conformation. The novel taxoid SB-T-2053 inhibits the growth of MCF-7 and LCC-6 human breast cancer cells (wild-type and drug resistant) on the same order of magnitude as paclitaxel. Moreover, SB-T-2053 induces in vitro tubulin polymerization at least as well as paclitaxel, which directly validates our drug design process. These results open a new avenue for drug design of next generation taxoids and other microtubule-stabilizing agents based on the refined structural information of drug-tubulin complexes, in accordance with typical enzyme-inhibitor medicinal chemistry precepts. 相似文献