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981.
The invention of atomic force microscopy (AFM) enabled us to study the statistical properties of single polymer chains by a method called "nanofishing," which stretches a single polymer chain adsorbed on a substrate with its one end by picking it at the other end. A force-extension curve obtained for a single polystyrene chain in a Theta solvent (cyclohexane) shows good agreement with a worm-like chain model and, therefore, gives microscopic information about entropic elasticity. Furthermore, the nanofishing technique can be used for dynamic viscoelastic measurement of single polymer chains. An AFM cantilever is mechanically oscillated at its resonant frequency during the stretching process. This technique enables the estimation of quantitative and simultaneous elongation-dependent changes of stiffness and viscosity of a single chain with the use of a phenomenological model. In this study, the effect of solvent on viscosity in low extension regions reveals that the viscosity is attributed to monomer-solvent friction. Thus, static and dynamic nanofishing techniques are shown to give powerful experimental proofs for several basic questions in polymer physics. The techniques are expected to reveal hidden properties of polymer chains or polymer solutions by any types of macroscopic measurements in the future. 相似文献
982.
Zhu KY Fu Q Xie HQ Xu SL Cheung AW Zheng KY Luk WK Choi RC Lau DT Dong TT Jiang ZY Chen JJ Tsim KW 《Journal of separation science》2010,33(23-24):3666-3674
Kaixinsan is an ancient Chinese herbal decoction mainly prescribed for patients suffering from mental depression. This decoction was created by Sun Si-miao of Tang Dynasty (A.D. 600) in ancient China, and was composed of four herbs: Radix and Rhizome Ginseng, Radix Polygalae, Rhizoma Acori Tatarinowii and Poria. Historically, this decoction has three different formulations, each recorded at a different point in time. In this study, the chemical compositions of all three Kaixinsan formulae were analyzed. By using rapid resolution LC coupled with a diode-array detector and an ESI triple quadrupole tandem MS (QQQ-MS/MS), the Radix and Rhizome Ginseng-derived ginsenosides including Rb(1), Rd, Re, Rg(1), the Radix Polygalae-derived 3,6'-disinapoyl sucrose, the Rhizoma Acori Tatarinowii-derived α- and β-asarone and the Poria-derived pachymic acid were compared among the three different formulations. The results showed variations in the solubility of different chemicals between one formula and the others. This systematic method developed could be used for the quality assessment of this herbal decoction. 相似文献
983.
Morikawa K Tanaka K Li F Awale S Tezuka Y Nobukawa T Kadota S 《Natural product communications》2010,5(10):1551-1556
The fragmentation pathways of seven types of taxoids were investigated by using a LC-MS/MS method, namely: (1) neutral taxoids with a C-4(20) double bond; (2) taxoids with a C-4(20) double bond and oxygenation at C-14; (3) 5-cinnamoyl taxoids with a C-4(20) double bond; (4) a basic taxoid with a C-4(20) double bond; (5) a taxoid with a C-4(20) epoxide; (6) taxoids with an oxetane ring; and (7) taxoids with an oxetane ring and a phenylisoserine C-13 side chain. Depending on the class of core structure and the substitution pattern, each taxoid gave either the molecular adduct ion [M+NH4]+ or [M+H]+. In the MS/MS, the molecular adduct ion gave characteristic product ions corresponding to the loss of water, acetic acid, benzoic acid, and cinnamic acid or the phenylisoserine group. These could reflect the difference of the substitutions and structural modifications and should be utilized for the structure elucidation oftaxoids by LC-MS. 相似文献
984.
Dr. Shiyao Liu Dr. Yoshiaki Tanabe Dr. Shogo Kuriyama Prof. Ken Sakata Prof. Yoshiaki Nishibayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(63):15650-15659
Ruthenium- and copper-catalyzed propargylic substitution reactions of propargylic alcohol derivatives with N-monosubstituted hydrazones as ambident nucleophiles are achieved in which N-monosubstituted hydrazones exhibit impressive different reactivities depending on different catalytic systems, behaving as carbon-centered nucleophiles to give the corresponding propargylic alkylated products in ruthenium catalysis, or as nitrogen-centered nucleophiles to afford the corresponding propargylic aminated products in copper catalysis. DFT calculations were carried out to investigate the detailed reaction pathways of these two systems. Further transformation of propargylic substituted products affords the corresponding multisubstituted pyrazoles as cyclization products in good to high yields. 相似文献
985.
Guanglong Su Connor J. Thomson Ken Yamazaki Daniel Rozsar Kirsten E. Christensen Trevor A. Hamlin Darren J. Dixon 《Chemical science》2021,12(17):6064
An efficient synthesis of enantioenriched hydroquinazoline cores via a novel bifunctional iminophosphorane squaramide catalyzed intramolecular aza-Michael reaction of urea-linked α,β-unsaturated esters is described. The methodology exhibits a high degree of functional group tolerance around the forming hydroquinazoline aryl core and wide structural variance on the nucleophilic N atom of the urea moiety. Excellent yields (up to 99%) and high enantioselectivities (up to 97 : 3 er) using both aromatic and less acidic aliphatic ureas were realized. The potential industrial applicability of the transformation was demonstrated in a 20 mmol scale-up experiment using an adjusted catalyst loading of 2 mol%. The origin of enantioselectivity and reactivity enhancement provided by the squaramide motif has been uncovered computationally using density functional theory (DFT) calculations, combined with the activation strain model (ASM) and energy decomposition analysis (EDA).The activation of both aromatic and aliphatic ureas as N-centered nucleophiles in intramolecular Michael addition reactions to α,β-unsaturated esters was achieved under bifunctional iminophosphorane squaramide superbase catalysis. 相似文献
986.
Yoshitaro Miyashita Nagina Mahboob Satoko Tsuboi Yasunori Yamada Kiyoshi Fujisawa Ken‐ichi Okamoto 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(5):558-559
The Re atom in [Re(C9H6N2)Cl3(C18H15P)] is octahedrally coordinated by three Cl atoms in facial positions, two N atoms from 8‐imidoquinoline (imq) and one P atom from triphenylphosphine. The Re—N(imido) distance [1.760 (9) and 1.772 (8) Å] for imq is very short and implies double‐bond character. The trans influence of the P atom is indicated. Intra‐ and intermolecular π–π interactions between the π‐rings in the complex are also observed. 相似文献
987.
988.
989.
Ken‐ichi Nakashima Naohito Abe Fumiko Kamiya Tetsuro Ito Masayoshi Oyama Munekazu Iinuma 《Helvetica chimica acta》2009,92(10):1999-2008
The three novel methylene bis[flavonoids] 1 – 3 , the novel 2‐flavene 4 , the new naturally occurring flavan 5 , and the new retro‐dihydrochalcone 6 were isolated from dragon's blood of Daemonorops draco, together with seven known compounds. The structures were elucidated by extensive 1D‐ and 2D‐NMR spectroscopic analysis. 相似文献
990.
Shigeru Furuichi Ken Kuriyama Kenjiro Yanagi 《Linear algebra and its applications》2009,430(8-9):2271-2276
In this short paper, we study some trace inequalities of the products of the matrices and the power of matrices by the use of elementary calculations. 相似文献