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961.
Nakata M Braams BJ Fukuda M Percus JK Yamashita M Zhao Z 《The Journal of chemical physics》2006,125(24):244109
Calculations on small molecular systems indicate that the variational approach employing the two-particle reduced density matrix (2-RDM) as the basic unknown and applying the P, Q, G, T1, and T2 representability conditions provides an accuracy that is competitive with the best standard ab initio methods of quantum chemistry. However, in this paper we consider a simple class of Hamiltonians for which an exact ground state wave function can be written as a single Slater determinant and yet the same 2-RDM approach gives a drastically nonrepresentable result. This shows the need for stronger representability conditions than the mentioned ones. 相似文献
962.
Dr. Hiroaki Itoh Kensuke Miura Koichi Kamiya Dr. Tomoya Yamashita Prof. Dr. Masayuki Inoue 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(11):4594-4601
We report a solid-phase strategy for total synthesis of the peptidic natural product yaku'amide B ( 1 ), which exhibits antiproliferative activity against various cancer cells. Its linear tridecapeptide sequence bears four β,β-dialkylated α,β-dehydroamino acid residues and is capped with an N-terminal acyl group (NTA) and a C-terminal amine (CTA). To realize the Fmoc-based solid-phase synthesis of this complex structure, we developed new methods for enamide formation, enamide deprotection, and C-terminal modification. First, traceless Staudinger ligation enabled enamide formation between sterically encumbered alkenyl azides and newly designed phosphinophenol esters. Second, application of Eu(OTf)3 led to chemoselective removal of the enamide Boc groups without detaching the resin linker. Finally, resin-cleavage and C-terminus modification were simultaneously achieved with an ester–amide exchange reaction using CTA and AlMe3 to deliver 1 in 9.1 % overall yield (24 steps from the resin). 相似文献
963.
Dr. Hiromichi Egami Taiki Rouno Tomoki Niwa Kousuke Masuda Dr. Kenji Yamashita Prof. Dr. Yoshitaka Hamashima 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(33):14205-14209
A linked dicarboxylate phase-transfer catalyst enables smooth asymmetric dearomative fluorination of 2-naphthols with Selectfluor under mild conditions to give the corresponding 1-fluoronaphthalenone derivatives in a highly enantioselective manner. This reaction, which is compatible with a range of functional groups, is the first example of catalytic asymmetric fluorination of 2-naphthols, and is expected to be useful in the synthesis of bioactive molecules. 相似文献
964.
The hexadentate nitrogen ligands 1-isoTQEN ( N,N,N',N'-tetrakis(1-isoquinolylmethyl)ethylenediamine) and 3-isoTQEN ( N,N,N',N'-tetrakis(3-isoquinolylmethyl)ethylenediamine) have been prepared. The structures of these ligands are based on that of TPEN ( N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine). The introduction of a benzene ring into TPEN affords fluorescence ability upon zinc-ion binding. Compared to the quinoline isomer TQEN, isoquinoline derivatives 1-isoTQEN and 3-isoTQEN exhibit a lower-energy shift in the excitation and emission wavelengths and an enhanced fluorescence intensity, probably because of the energy-transfer mechanism between adjacent isoquinoline rings. Importantly, an increase in the Zn (2+)/Cd (2+) discriminating ability and a reduction in the background fluorescence induced by pH were also achieved for isoquinoline derivatives. The zinc-ion-induced fluorescence of these isoTQENs was not quenched by an addition of TPEN, which demonstrates the significantly high zinc-ion binding ability of these isoTQEN ligands. 相似文献
965.
An efficient synthesis of the pentacyclic framework of cortistatins has been developed. The key strategy comprises assembly of the A- and the CD-ring fragments by Knoevenagel reaction, facile formation of the pyran ring via electrocyclization, and construction of the seven-membered B-ring by radical addition to an alpha,beta-unsaturated ketone. 相似文献
966.
Nobuto Yoshinari Natthaya Meundaeng Hiroyasu Tabe Yusuke Yamada Satoshi Yamashita Yasuhiro Nakazawa Takumi Konno 《Angewandte Chemie (International ed. in English)》2020,59(41):18048-18053
Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single‐crystal‐to‐single‐crystal (SCSC) transformation is presented. Soaking single crystals of K6[Rh4Zn4O(l ‐cys)12] (K6[ 1 ]; l ‐H2cys=l ‐cysteine) in a water/ethanol solution containing Ln(OAc)3 (Ln3+=lanthanide ion) results in the exchange of K+ by Ln3+ with retention of the single crystallinity, producing Ln2[ 1 ] ( 2Ln ) and Ln0.33[Ln4(OH)4(OAc)3(H2O)7][ 1 ] ( 3Ln ) for early and late lanthanides, respectively. While the Ln3+ ions in 2Ln exist as disordered aqua species, those in 3Ln form ordered hydroxide‐bridged cubane clusters that connect [ 1 ]6? anions in a 3D metal‐organic framework through coordination bonds with carboxylate groups. This study shows the utility of an anionic metallosupramolecular framework with carboxylate groups for the creation of a series of metal cubanes that have great potential for various applications, such as magnetic materials and heterogeneous catalysts. 相似文献
967.
Dr. Nobuto Yoshinari Dr. Natthaya Meundaeng Dr. Hiroyasu Tabe Prof. Yusuke Yamada Dr. Satoshi Yamashita Prof. Yasuhiro Nakazawa Prof. Takumi Konno 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18204-18209
Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single-crystal-to-single-crystal (SCSC) transformation is presented. Soaking single crystals of K6[Rh4Zn4O(l -cys)12] (K6[ 1 ]; l -H2cys=l -cysteine) in a water/ethanol solution containing Ln(OAc)3 (Ln3+=lanthanide ion) results in the exchange of K+ by Ln3+ with retention of the single crystallinity, producing Ln2[ 1 ] ( 2Ln ) and Ln0.33[Ln4(OH)4(OAc)3(H2O)7][ 1 ] ( 3Ln ) for early and late lanthanides, respectively. While the Ln3+ ions in 2Ln exist as disordered aqua species, those in 3Ln form ordered hydroxide-bridged cubane clusters that connect [ 1 ]6− anions in a 3D metal-organic framework through coordination bonds with carboxylate groups. This study shows the utility of an anionic metallosupramolecular framework with carboxylate groups for the creation of a series of metal cubanes that have great potential for various applications, such as magnetic materials and heterogeneous catalysts. 相似文献
968.
Perfluorinated surfactants of heptafluorobutylate and pentadecafluorooctanoate ions were adsorbed on an activated charcoal cartridge and decomposed with sodium biphenyl (SBP) reagent to form inorganic fluoride ion. The fluoride ion thus formed was determined by flow injection analysis (FIA) using quercetin-Zr complex as a fluorimetric reagent, where λex and λem were 422 and 491 nm, respectively. The limit of detection for fluoride ion by the FIA system was developed to 1.1 × 10−6 M (signal to noise ratio of three), when 50% (v/v) tetrahydrofuran (THF) was used as a dissolving solvent for quercetin. The perfluorinated surfactants in the sample solution were quantitatively adsorbed on the cartridge containing 100 mg of activated charcoal and were decomposed with 0.5 mL of sodium biphenyl reagent after drying thoroughly by flowing through dry nitrogen gas. The fluoride ion formed was recovered with 3 mL of purified water as an eluent, and it was determined by the fluorimetric flow injection system. The blank fluorescence signal accompanied during the adsorption/decomposition on the cartridge was reduced by washing the activated charcoal with acetone. The blank signal was also observed from dimethoxyethane, which was used in sodium biphenyl reagent. When 600 mL sample solution was used and 200 times enrichment was applied, the heptafluorobutylate and pentadecafluorooctanoate ions at the concentrations of 2.1 μg L−1 were quantitatively recovered as fluoride ion, and the limit of detections for the perfluorinated surfactants were 0.3 and 0.3 μg L−1 for the two perfluorinated surfactants, respectively (3 sigma of the blank signal). 相似文献
969.
970.
Hashimoto S Fujimori T Tanaka H Urita K Ohba T Kanoh H Itoh T Asai M Sakamoto H Niimura S Endo M Rodriguez-Reinoso F Kaneko K 《Journal of the American Chemical Society》2011,133(7):2022-2024
Vibrational-rotational properties of CH(4) adsorbed on the nanopores of single-wall carbon nanohorns (SWCNHs) at 105-140 K were investigated using IR spectroscopy. The difference vibrational-rotational bands of the ν(3) and ν(4) modes below 130 K show suppression of the P and R branches, while the Q branches remain. The widths of the Q branches are much narrower than in the bulk gas phase due to suppression of the Doppler effect. These results indicate that the rotation of CH(4) confined in the nanospaces of SWCNHs is highly restricted, resulting in a rigid assembly structure, which is an anomaly in contrast to that in the bulk liquid phase. 相似文献