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101.
Yuki Kobayashi Yu Kojima Ryotaro Miki Toshinobu Seki Takashi Fujihara Yoshihiro Ishimaru Yuya Egawa 《Journal of inclusion phenomena and macrocyclic chemistry》2018,92(3-4):311-317
Herein, we have proposed a single-step preparation of topological gels using vinyl-modified β-cyclodextrin (V-β-CyD) and isoprene. Copolymerization of V-β-CyD and isoprene in an aqueous solution resulted in gelation due to V-β-CyD acting as a novel type of copolymer chain cross-linker. The vinyl moiety of V-β-CyD becomes a part of the copolymer, while the β-CyD moiety of V-β-CyD simultaneously incorporates the isoprene component of the copolymer. V-β-CyD is capable of two different modes of cross-linking at each end, i.e., chemically bonding and mechanically interlocking. Due to the shape of the cross-linking point, we refer to it as figure-of-six cross-linking. Nuclear magnetic resonance analysis showed that the gel contained V-β-CyD and isoprene in an approximately 1:0.3 stoichiometry. The relatively high content of β-CyD was reflected in the character of the gel; the gel swelled in dimethylformamide which is a good solvent of β-CyD. A fluorometric analysis using 6-(p-toluidino)-2-naphthalenesulfonic acid showed that the appended β-CyD was able to accommodate guest molecules. Introduction of an additional vinyl monomer into the gel was also successful. Addition of 4-vinylphenylboronic acid to the preparation procedure yielded a sugar-responsive gel that swelled in the presence of d-fructose. 相似文献
102.
An efficient ruthenium catalyst system for the direct ortho CH borylation of aromatic imines is described. The reaction of tert-butyl-1-arylmethanimines with pinacolborane in the presence of Ru(cod)(cot), followed by hydrolysis, to afford the ortho-formyl-substituted arylboronates. The borylation was achieved with complete mono-selectivity. 相似文献
103.
Poonam Gupta Dr. Durga Prasad Karothu Dr. Ejaz Ahmed Prof. Panče Naumov Prof. Naba K. Nath 《Angewandte Chemie (International ed. in English)》2018,57(28):8498-8502
The first example of a smart crystalline material, the 2:1 cocrystal of probenecid and 4,4′‐azopyridine, which responds reversibly to multiple external stimuli (heat, UV light, and mechanical pressure) by twisting, bending, and elastic deformation without fracture is reported. This material is also able to self‐heal on heating and cooling, thereby overcoming the main setbacks of molecular crystals for future applications as crystal actuators. The photo‐ and thermomechanical effects and self‐healing capabilities of the material are rooted in reversible trans–cis isomerization of the azopyridine unit and crystal‐to‐crystal phase transition. Fairly isotropic intermolecular interactions and interlocked crisscrossed molecular packing secure high elasticity of the crystals. 相似文献
104.
The total synthesis of myxol stereoisomers 1a,b and deoxymyxol (plectaniaxanthin) stereoisomers 2a,b was accomplished by Wittig reaction of (S)- and (R)-C10-phosphonium salts 8a,b bearing a silyl-protected 1,2-dihydroxy-ψ end group with C30-apocarotenals 6 and 7. The phosphonium salts 8a,b were derived from aldehydes 11a,b possessing a cyclopentylidene ketal moiety, prepared via Sharpless asymmetric epoxidation of allylic alcohol 12 followed by regioselective cleavage of the oxirane ring. We established an analytical HPLC method using a chiral column to separate stereoisomers 1a,b and 2a,b and thus determined the absolute configurations of the natural products. The HPLC analyses established that both myxol and deoxymyxol isolated from bacteria have the 2′S-configuration. 相似文献
105.
We apply our previously developed deconvolution method and interpretation to analyze changes in the OH stretching band [ν(OH) band] of low‐concentration (≤0.2 m) aqueous solutions of NaCl and KCl. We treat these simple, monovalent ions as defects in the hydrogen‐bond network of pure water and quantify the changes in the spectra at low defect concentration with an “order parameter”. Order‐parameter analysis of difference spectra of the two solutions leads to hydration numbers of 7.0±1.0 and 5.9±0.3 for K+ and Na+, respectively. Additionally, we find that changes in the ν(OH) band due to low concentrations of ions result from changes in the topology of the hydrogen‐bond network. 相似文献
106.
The first enantioselective total synthesis of (+)-sarcodictyenone is described [4.3% overall yield from (5R,6R)-6-methyl-5-trimethylsily-2-cyclohexenone]. This work establishes the absolute stereochemistry of the natural product. 相似文献
107.
Copper-catalyzed reactions of carbonyl-ene-nitriles with carbon nucleophiles, such as aromatics and ketones, afforded pyrrolin-2-ones (gamma-lactam) in excellent yield. The reaction mechanism involves addition reactions with a ketimine moiety of the 2-aza-2,4-cyclopentadienone intermediate, which is formed via hydration of a nitrile moiety followed by dehydrative cyclization. 相似文献
108.
109.
Determination and purification of sesamin and sesamolin in sesame seed oil unsaponified matter using reversed‐phase liquid chromatography coupled with photodiode array and tandem mass spectrometry and high‐speed countercurrent chromatography
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Miki Takahashi Yuzo Nishizaki Naoki Sugimoto Hiroaki Takeuchi Kazuya Nakagawa Hiroshi Akiyama Kyoko Sato Koichi Inoue 《Journal of separation science》2016,39(20):3898-3905
In Asian countries, sesame seed oil unsaponified matter is used as a natural food additive due to its associated antioxidant effects. We determined and purified the primary lignans sesamin and sesamolin in sesame seed oil unsaponified matter using reversed‐phase liquid chromatography coupled with photodiode array and tandem mass spectrometry and high‐speed countercurrent chromatography. Calibration curves showed good correlation coefficients (r2 > 0.999, range 0.08 and/or 0.15 to 5 μg/mL) with a limit of detection (at 290 nm) of 0.02 μg/mL for sesamin and 0.04 μg/mL for sesamolin. Sesame seed oil unsaponified matter contained 2.82% sesamin and 2.54% sesamolin, respectively. Direct qualitative analysis of sesamin and sesamolin was achieved using quadrupole mass spectrometry with positive‐mode electrospray ionization. Pure (>99%) sesamin and sesamolin standards were obtained using high‐speed countercurrent chromatographic purification (hexane/ethyl acetate/methanol/water; 7:3:7:3). An effective method for determining and purifying sesamin and sesamolin from sesame seed oil unsaponified matter was developed by combining these separation techniques for standardized food additives. 相似文献
110.
Tanaka D Horike S Kitagawa S Ohba M Hasegawa M Ozawa Y Toriumi K 《Chemical communications (Cambridge, England)》2007,(30):3142-3144
Confinement of electron donor guests affords an efficient, photo-induced charge transfer (CT) with the anthracene moieties of a porous coordination polymer. 相似文献