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1.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity
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Yohei Ohkoda Akane Asaishi Tomoya Namiki Tomoaki Hashimoto Midori Yamada Koichiro Shirai Yuta Katagami Dr. Tomoaki Sugaya Prof. Makoto Tadokoro Prof. Akiharu Satake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11745-11756
The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η3‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η3‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands. 相似文献
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3.
K. Kitamura Hideyuki Mano Yoshie Shimamoto Yoshihiro Tadokoro Koji Tsuruta Shinji Kitagawa 《Analytical and bioanalytical chemistry》1997,358(4):509-513
The second-derivative spectra of chlorpromazine (CPZ) or triflupromazine (TFZ) in buffer solutions (pH 7.4) containing various amounts of BSA (the reference solutions contained the same amount of BSA) showed derivative isosbestic points. The residual background signals derived from incomplete suppression of BSA signals can be entirely eliminated in the second-derivative spectra and BSA has spectrophotometrically one kind of binding site for CPZ or TFZ. The fractions of the drugs bound to BSA were calculated from the derivative intensity differences (ΔD values) of CPZ or TFZ before and after the addition of BSA. Scatchard plot experiments suggested that the binding of the drugs to BSA could be explained as a partition like non-specific binding model. The association constants (K) of CPZ or TFZ with BSA were calculated from the ΔD values according to the non-specific binding model by a nonlinear least-squares method. The K values were almost constant for all of the drug concentrations studied, and good reproducibility was obtained. The fractions predicted by the K values were in good coincidence to the observed values. These results confirm the usefulness of the proposed derivative method which does not need any separation procedures. 相似文献
4.
Sekimoto Shun Tatenuma Katsuyoshi Suzuki Yumi Tsuguchi Akira Tanaka Atsushi Tadokoro Takahiro Kani Yuko Morikawa Yasumasa Yamamoto Asaki Ohtsuki Tsutomu 《Journal of Radioanalytical and Nuclear Chemistry》2017,311(2):1361-1366
The medical radionuclide 99Mo was produced by the 100Mo(γ,n) reaction using bremsstrahlung photons generated by an electron linear accelerator. The amount of 99Mo produced was compared to that predicted by calculation using the particles and heavy ion transport code system. From the 99Mo produced, highly pure 99mTc was separated using the so-called technetium master milker, and the chemical yield of 99mTc was 83–99 %. The installation of a new complex using this method and the electron linear accelerator with the preferable specification was suggested, and a possibility to supply the demand of 99mTc was discussed and shown.
相似文献5.
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Natsuki Yamashita Atsuhito Tadokoro Eiichiozu Toshihisa Maeshima Ion C. Baianu Lun-Shin Wei 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1223-1239
The anionic polymerization of acrolein (AL) with N, N-dimethylamino-propylacrylamide (DMAPA) in the presence of water was investigated in tetrahydrofuran, benzene, and ethanol at 0°C in a nitrogen atmosphere. The resulting polymers were found to be essentially vinyl polymers with one DMAPA attached and an aldehyde side chain. From observations of the polymerization process by 1H NMR, we find that polymerization was initiated by the hydroxyl anion formed in the thermodynamic equilibrium between the amine of DMAPA and water. The hydrogen transfer reaction of DMAPA was caused by the propagating poly-AL anion. On the other hand, the monomer reactivity ratios and the Q2-e2values of DMAPA were determined by the free-radical copolymerization of styrene (St, M1) with DMAPA and AIBN as initiator. 相似文献
7.
Inagaki Makoto Sekimoto Shun Tadokoro Takahiro Ueno Yuichiro Kani Yuko Ohtsuki Tsutomu 《Journal of Radioanalytical and Nuclear Chemistry》2020,324(2):681-686
Journal of Radioanalytical and Nuclear Chemistry - Amount estimation of production of 99Mo required for medical applications was carried out by utilizing an electron linear accelerator with... 相似文献
8.
Prof. Makoto Tadokoro Masaki Itoh Ryota Nishimura Kensuke Sekiguchi Dr. Norihisa Hoshino Dr. Hajime Kamebuchi Prof. Jun Miyazaki Dr. Fumiya Kobayashi Prof. Motohiro Mizuno Prof. Tomoyuki Akutagawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201397
A new H-bonded crystal [RuIII(Him)3(Im)3] with three imidazole (Him) and three imidazolate (Im−) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the RuIII complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10−5 S cm−1 at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [RuIII(Him)3(Im)3] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state 2H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered. 相似文献
9.
Tsuyoshi Satoh Takayuki Kuramoto Shingo Ogata Hiroyuki Watanabe Takahito Saitou Makoto Tadokoro 《Tetrahedron: Asymmetry》2010,21(1):1-5
Treatment of enantiomerically pure 1-chlorovinyl p-tolyl sulfoxides, derived from cyclic ketones and (R)-chloromethyl p-tolyl sulfoxide, with the lithium enolate of tert-butyl carboxylates gave adducts in quantitative yields as single diastereomers. The adducts were treated with i-PrMgCl in toluene to afford optically active bicyclo[n.1.0]alkanes bearing a tert-butyl carboxylate moiety in up to 99% enantiomeric excess through the enantioselective 1,3-CH insertion reaction of the generated chiral magnesium carbenoids. This is the first example of the enantioselective 1,3-CH insertion reaction of magnesium carbenoid. 相似文献
10.
Yasuyuki Tanaka Yasumasa Takeuchi Masamichi Kobayashi Hiroyuki Tadokoro 《Journal of Polymer Science.Polymer Physics》1971,9(1):43-57
Extinction coefficients of the characteristic infrared bands due to isomeric structural units were measured for polybutadiene and polyisoprene in CS2 or CCl4 solutions and were compared with the isomer composition determined by NMR. The NMR signal assignments were made on the basis of the spectra of deutero derivatives of the polymers. In the case of polyisoprene, linear relations were obtained between the extinction coefficients and the isomer contents determined by NMR for the absorption bands at 1385 cm?1 (characteristic of trans-1,4 units), 1376 cm?1 (cis-1,4 units), and 889 cm?1 (3,4 units). However, for the absorption bands at 840 cm?1 (characteristic of cis-1,4 and trans-1,4 units), isomerized polyisoprenes did not give such a linear relationship. In polybutadiene, the extinction coefficient for the atactic 1,2 units was found to be lower than that of the syndiotactic 1,2 unit. These experimental facts lead to the conclusion that additivity of the extinction coefficients does not always hold for diene polymers. The deviation from the linear relation may be associated with regular sequences of one isomeric conformation in the chain. 相似文献