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61.
Robust Inclusion Complexes of Crown Ether Fused Tetrathiafulvalenes with Li+@C60 to Afford Efficient Photodriven Charge Separation 下载免费PDF全文
Dr. Mustafa Supur Yuki Kawashima Dr. Karina R. Larsen Dr. Kei Ohkubo Prof. Jan O. Jeppesen Prof. Shunichi Fukuzumi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):13976-13983
Inclusion complexes of benzo‐ and dithiabenzo‐crown ether functionalized monopyrrolotetrathiafulvalene (MPTTF) molecules were formed with Li+@C60 ( 1? Li+@C60 and 2? Li+@C60). The strong complexation has been quantified by high binding constants that exceed 106 M ?1 obtained by UV/Vis titrations in benzonitrile (PhCN) at room temperature. On the basis of DFT studies at the B3LYP/6‐311G(d,p) level, the orbital interactions between the crown ether moieties and the π surface of the fullerene together with the endohedral Li+ have a crucial role in robust complex formation. Interestingly, complexation of Li+@C60 with crown ethers accelerates the intersystem crossing upon photoexcitation of the complex, thereby yielding 3(Li+@C60)*, when no charge separation by means of 1Li+@C60* occurs. Photoinduced charge separation by means of 3Li+@C60* with lifetimes of 135 and 120 μs for 1? Li+@C60 and 2? Li+@C60, respectively, and quantum yields of 0.82 in PhCN have been observed by utilizing time‐resolved transient absorption spectroscopy and then confirmed by electron paramagnetic resonance measurements at 4 K. The difference in crown ether structures affects the binding constant and the rates of photoinduced electron‐transfer events in the corresponding complex. 相似文献
62.
Prof. Yutaka Maeda Yuhei Hasuike Prof. Kei Ohkubo Atsushi Tashiro Shinya Kaneko Masayuki Kikuta Dr. Michio Yamada Prof. Tadashi Hasegawa Prof. Takeshi Akasaka Dr. Jing Zhou Prof. Jing Lu Prof. Shigeru Nagase Prof. Shunichi Fukuzumi 《Chemphyschem》2014,15(9):1821-1826
This report describes the photochemical behavior of single‐walled carbon nanotubes (SWNTs) in the presence of propylamine. The SWNTs are characterized by absorption and Raman spectroscopy. The spectral changes due to photoirradiation indicate that reactions occur predominantly with the metallic SWNTs and small‐diameter SWNTs. The detection of amine radicalcation species by ESR spectroscopy reveals photoinduced electron transfer from the amine to the excited SWNTs. After exposure of the photoirradiated SWNTs to air, the characteristic spectra were recovered, except for that of the small‐diameter SWNTs. The results suggest that, after photoreduction of the SWNTs, subsequent selective sidewall functionalization of the small‐diameter SWNTs occurs. 相似文献
63.
Kei Fujise Eiji Tsurumaki Gaku Fukuhara Nobuyuki Hara Yoshitane Imai Shinji Toyota 《化学:亚洲杂志》2020,15(16):2456-2461
Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π‐conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt‐catalyzed cycloisomerization of the corresponding ethynyl‐substituted precursors. The nonplanar and helical structure was confirmed by X‐ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol?1. The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δ?| 1380 L mol?1 cm?1) and CPL (|glum| 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time‐dependent DFT calculations. 相似文献
64.
Solubility Switching of Metallophthalocyanines and Their Larger Derivatives upon Encapsulation 下载免费PDF全文
Dr. Kei Kondo Prof. Dr. Munetaka Akita Dr. Michito Yoshizawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1937-1940
Metallophthalocyanines (MPcs) are very useful pigments but scarcely soluble without appropriate functional groups in common solvents. Herein, we report that bent polyaromatic amphiphiles act as excellent solubilizing reagents for nonfunctionalized MPcs and larger MPc derivatives (e.g., CuPc, perhalogenated CuPcs, Cu‐naphthalocyanine, CuPc polymers, and double‐decker MPcs) in neutral water upon encapsulation. The resultant MPc nanocomposites display high stability towards heat and pH change. More importantly, the encapsulated MPcs can be released by simple protocols under mild conditions both into a bulk solvent and onto glass or polymer plates. 相似文献
65.
66.
To develop a sensitive and selective chemiluminometric method for the determination of methylglyoxal, we used 2-aminonicotinic acid as the chemiluminescence derivatization reagent. 2-Aminonicotinic acid reacts with methylglyoxal in an acidic solution at 37 degrees C for 4 h and gave a chemiluminescence in N,N'-dimethylformamide containing sodium tert-butoxide. The detection limit (blank intensity plus three-times its standard deviation of methylglyoxal) for methylglyoxal is 233 fmol in the reaction mixture. 相似文献
67.
Kei Matsuzaki Shuichi Okuzono Taiichi Kanai 《Journal of polymer science. Part A, Polymer chemistry》1979,17(11):3447-3458
α-Methylvinyl methyl ether, ethyl ether, and isobutyl ether were polymerized under various polymerization conditions and the structure of the polymers was determined by 1H- and 13C-NMR spectroscopy. α-Methyl and β-methylene carbon spectra of poly(α-methylvinyl isobutyl ether) showed splitting and were analyzed by triad and tetrad sequences. β-Methylene carbon spectra of poly(α-methylvinyl ethyl ether) also showed splitting. When Eu(fod)3 was added, α-methyl and methoxy proton spectra in benzene of poly(α-methylvinyl methyl ether) showed splitting assigned to triad tacticities. All the polymers obtained in polar solvents exhibited an increase in syndiotacticity. The polymerization mechanism is discussed. 相似文献
68.
A fluorimetric assay for lecithin-cholesterol acyltransferase in human plasma (normal and pathological) is described. The lowered cholesterol concentration in the enzyme reaction is determined fluorimetrically by using the cholesterol oxidase—peroxidase —tyramine system. The assay requires only 10 μl of plasma. 相似文献
69.
Eishun Tsuchida Yoshihito Osada Kei Sanada 《Journal of polymer science. Part A, Polymer chemistry》1972,10(11):3397-3404
The interaction between sodium poly(styrene sulfonate) (NaSS) and side-chain charged polycation polymer (pendent type) or main-chain charged polycation polymer (integral type) has been studied. It was found that the polyion complex (the reaction product of these polyelectrolytes) of pendent–pendent type has an equimolar composition at any mixing ratio of two component polymers. However, a polyion complex of integral–pendent type can form a water-soluble complex with a ratio of [polycation]/[polyanion] = 1/3, in addition to a complex with a equimolar composition. The mechanism of formation of this specific complex is discussed. 相似文献
70.