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121.
Yuji Kikukawa Kensuke Seto Daiki Watanabe Hiromasa Kitajima Misaki Katayama Shohei Yamashita Yasuhiro Inada Yoshihito Hayashi 《Angewandte Chemie (International ed. in English)》2020,59(34):14399-14403
Dodecavanadate, [V12O32]4? (V12), possesses a 4.4 Å cavity entrance, and the cavity shows unique electrophilicity. Owing to the high polarizability, Br2 was inserted into V12, inducing the inversion of one of the VO5 square pyramids to form [V12O32(Br2)]4? (V12(Br2)). The inserted Br2 molecule was polarized and showed a peak at 185 cm?1 in the IR spectrum. The reaction of V12(Br2) and toluene yielded bromination of toluene at the ring, showing the electrophilicity of the inserted Br2 molecule. Compound V12(Br2) also reacted with propane, n‐butane, and n‐pentane to give brominated alkanes. Bromination with V12(Br2) showed high selectivity for 3‐bromopentane (64 %) among the monobromopentane products and preferred threo isomer among 2‐,3‐dibromobutane and 2,3‐dibromopenane. The unique inorganic cavity traps Br2 leading the polarization of the diatomic molecule. Owing to its new reaction field, the trapped Br2 shows selective functionalization of alkanes. 相似文献
122.
Hayate Saito Keita Yamamoto Yosuke Sumiya Ling‐Jun Liu Keisuke Nogi Satoshi Maeda Hideki Yorimitsu 《化学:亚洲杂志》2020,15(16):2442-2446
C?H iodination of aromatic compounds has been accomplished with the aid of sulfinyl directing groups under palladium catalysis. The reaction proceeds selectively at the peri‐position of polycyclic aryl sulfoxides or at the ortho‐position of phenyl sulfoxides. The iodination products can be further converted via iterative catalytic cross‐coupling at the expense of the C?I and C?S bonds. Computational studies suggest that peri‐C?H palladation would proceed via a non‐directed pathway, wherein neither of the sulfur nor oxygen atom of the sulfinyl group coordinates to the palladium before and at the transition state. 相似文献
123.
124.
Tolerance bioaccumulation and biotransformation of arsenic compounds by a freshwater prawn (Macrobrachium rosenbergii) were investigated. M. rosenbergii was exposed to 10, 20, 30 and 35 μg As cm−3 of disodium arsenate [abbreviated as As(V)], 25, 50, 100 and 120 μg As cm−3 of methylarsonic acid (MMAA), or 100,200, 300 and 350 μg As cm−3 of dimethylarsinic acid (DMAA). Tolerances (50% lethal concentration: LC50) of the prawn against As(V), MMAA, and DMAA were 30, 100, and 300 μg As cm−3, respectively. The prawn accumulated arsenic compounds directly from aqueous phase and biotransformed them in part. Both methylation and demethylation of the arsenicals were observed in vivo. Highly methylated and less toxic arsenicals were less accumulated in M. rosenbergii. 相似文献
125.
Shigeyoshí Nishino Yasuhiro Nagato Yoshihiro Hasegawa Hisanao Yamamoto Kazuo Kamaike Yoshiharu Ishido 《Heteroatom Chemistry》1991,2(1):187-196
Reagent systems of sodium– and tetrabutylammonium nitrite–acetic anhydride were proved to be extremely efficient for the deanilidation of nucleoside 3′-phosphoranilidates, whose reactions were rapid with the former and instant with the latter. It was further found that the reagent system is applicable to oligonucleotide synthesis provided that the exocyclic amino groups of 2′-deoxyadenosine, 2′-deoxyguanosine, and 2′-deoxycytidine were protected by succinylation. 相似文献
126.
Shoichi Maeda Shunta Chikami Glenn Villena Latag Subin Song Norio Iwakiri Tomohiro Hayashi 《Molecules (Basel, Switzerland)》2022,27(7)
In this paper, we propose a new spectroscopic method to explore the behavior of molecules near polymeric molecular networks of water-containing soft materials such as hydrogels. We demonstrate the analysis of hydrogen bonding states of water in the vicinity of hydrogels (soft contact lenses). In this method, we apply force to hydrated contact lenses to deform them and to modulate the ratio between the signals from bulk and vicinal regions. We then collect spectra at different forces. Finally, we extracted the spectra of the vicinal region using the multivariate curve resolution-alternating least square (MCR-ALS) method. We report the hydration states depending on the chemical structures of hydrogels constituting the contact lenses. 相似文献
127.
128.
Deguchi K Keira T Yamada K Ito H Takegawa Y Nakagawa H Nishimura S 《Journal of chromatography. A》2008,1189(1-2):169-174
A novel chromatographic approach coupling anion-exchange (diethylaminoethylene) and hydrophilic-interaction (amide or zwitterionic type) columns was developed for the separating of 2-pyridylamino derivatives of N-glycans (PA-N-glycans). This is a kind of on-line, two-dimensional (2D) separation approach in hydrophilic-interaction chromatography (called the 2D-HILIC method), analogous to that of coupling cation- (or anion-, or mixed ion-) exchange and reversed-phase columns in hydrophobic interaction (reversed-phase) chromatography. The efficiency of the 2D-HILIC method was tested with biantennary neutral and sialylated PA-N-glycan standards by properly combining linear gradient elutions of water-acetonitrile and spiked-salt (ammonium acetate) elutions. The retention time RSDs of all the peaks in three sequential runs of a 100 min cycle are less than 0.52%, which indicates a reasonably good repeatability of the 2D-HILIC method. Then, the method was applied to a complex mixture of PA-N-glycans from human serum proteins. It was demonstrated that the neutral PA-N-glycans and mono-, di-, tri-, and tetrasialylated PA-N-glycans are able to be eluted in turn according to the number of sialic acids in an automated (programmed) single run. 相似文献
129.
以廉价、低毒的醋酸亚铁为催化剂,在三氟乙酸助催化下,2-甲基氮杂芳烃与芳香醛经过加成与脱水反应,直接选择性合成具有生物活性的反式2-烯基氮杂芳烃化合物,水是唯一副产物.该合成方法催化剂用量少,后处理方便,产率高,选择性高,底物适用范围广.治疗哮喘药顺尔丁中间体(E)-3-[2-(7-氯-2-喹啉基)乙烯基]苯甲醛(3v)的克级合成展现了该方法的应用前景. 相似文献
130.
Dr. Atsuko Masuya-Suzuki Satoshi Goto Takafumi Kambe Dr. Ryunosuke Karashimada Dr. Yasuhiro Kubota Prof. Nobuhiko Iki 《ChemistryOpen》2021,10(1):46-55
We prepared Ln(III) (Ln=Eu, Gd, and Yb) complexes with a tripodal Schiff base, tris[2-(5-methylsalicylideneimino)ethyl]amine (H3L) and studied their photophysical properties. Upon ligand excitation, YbL showed Yb(III)-centered luminescence in the near-infrared region. While the overall quantum yield (0.60(1)%) of YbL in acetonitrile was moderate among the reported values for Yb(III) complexes, its radiative lifetime (0.33(2) ms) was significantly shorter than those reported previously. We propose that the ligand-to-metal charge-transfer (LMCT) state mediated the sensitization in YbL. The emission and excitation spectra of EuL indicated the participation of the LMCT state in the sensitization. The radiative lifetime (0.84(7) ms) for EuL in the solid state was rather short compared to those of reported Eu(III) complexes. Our results show that the Yb(III) complex with the Schiff base ligand has two features: the short radiative lifetime and the non-triplet sensitization path. 相似文献