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31.
In single‐molecule force spectroscopy (SMFS), many studies have focused on the elasticity and conformation of polymer chains, but little attention has been devoted to the dynamic properties of single polymer chains. In this study, we measured the energy dissipation and elastic properties of single polystyrene (PS) chains in toluene, methanol, and N,N‐dimethylformamide using a homemade piezo‐control and data acquisition system externally coupled to a commercial atomic force microscope (AFM), which provided more accurate information regarding the dynamic properties of the PS chains. We quantitatively measured the chain length‐dependent changes in the stiffness and viscosity of a single chain using a phenomenological model consistent with the theory of viscoelasticity for polymer chains in dilute solution. The effective viscosity of a polymer chain can be determined using the Kirkwood model, which is independent of the intrinsic viscosity of the solvent and dependent on the interaction between the polymer and solvent. The results indicated that the viscosity of a single PS chain is dominated by the interaction between the polymer and solvent. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1736–1743 相似文献
32.
To prepare cross‐linked silicone (silicone rubber) particles in an aqueous medium, we investigated two synthesis methods involving a miniemulsion system. The first method was based on cationic ring‐opening polymerization of cyclic siloxane, which is a common synthetic route for linear silicone oil and uses octamethylcyclotetrasiloxane (D4) as the monomer and dimeric D4 (bis‐D4) as the cross‐linker. Although this method produces silicone particles, the particles do not remain in the particulate state after drying because of low cross‐linking density. The polymerization mechanism of this method was also investigated, which proceeds under the ring‐opening reaction of D4 in monomer droplets and upon polycondensation of hydrolyzed D4, which occurs in the water phase (ie, outside the monomer droplets). This mechanism implied that introducing the cross‐linking structure into particles is difficult because of the low solubility of bis‐D4 in water. To overcome these difficulties, we demonstrated a second method of preparing silicone particles based on the thiol‐Michael addition reaction between thiol‐terminated silicone oil and triacrylate in miniemulsion systems. Transmission electron microscopy images indicated that the silicone particles obtained in the particulate state upon drying and the aggregates of these particles showed elasticity. 相似文献
33.
Jin Tanaka Yu Shibata Anton Joseph Juntaro Nogami Jyunichi Terasawa Ryo Yoshimura Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(26):5774-5779
It has been established that a newly developed cyclopentadienyl rhodium(III) [CpARhIII] complex, bearing an acidic secondary amide moiety on the Cp ring, is able to catalyze the ortho-bromination of O-phenyl carbamates with N-bromosuccinimide (NBS) at room temperature. The presence of the acidic secondary amide moiety on the CpA ligand accelerates the bromination by the hydrogen bond between the acidic NH group of the CpA ligand and the carbonyl group of NBS. 相似文献
34.
Li-Hsiang Wang Norihiko Hayase Dr. Haruki Sugiyama Juntaro Nogami Prof. Dr. Hidehiro Uekusa Prof. Dr. Ken Tanaka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18107-18113
Single and double cyclophenylene–ethynylenes (CPEs) with axial and helical chirality have been synthesized by the Sonogashira cross-coupling of di- and tetraethynyl biphenyls with a U-shaped prearomatic diiodoparaphenylene followed by reductive aromatization. X-ray crystallographic analyses and DFT calculations revealed that the CPEs possess highly twisted bent structures. Bend angles on the edge of the paraphenylene units were close to the value of [5]cycloparaphenylene (CPP)—the smallest CPP to date. The double and single CPEs possessed stable chirality despite flexible biphenyl structures because of the high strain in the diethynyl–paraphenylene moiety. In both the single and double CPEs, orbital interactions along the biphenyl axis were observed by DFT calculations in LUMO and LUMO+2 of the single CPE and LUMO+1 of the double CPE, which likely cause lowering of these orbital energies. Concerning chiroptical properties: boosting of the gabs value was observed in the biphenyl-based double CPE, as well as the binaphthyl-based single CPE, compared to the biphenyl-based single CPE. 相似文献
35.
Yukimasa Aida Juntaro Nogami Dr. Haruki Sugiyama Prof. Dr. Hidehiro Uekusa Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12579-12588
The enantioselective synthesis of polycyclic aromatic hydrocarbon (PAH)-based planar chiral cyclophanes was achieved for the first time by the rhodium-catalyzed intramolecular regio- and enantioselective [2+2+2] cycloaddition of tethered diyne-benzofulvenes followed by stepwise oxidative transformations. The thus synthesized planar chiral bent cyclophanes, that possess bent p-terphenyl- and 9-fluorenone-cores, were converted to 9-fluorenol-based ones with excellent ee values of >99 % by diastereoselective 1,2-reduction. These 9-fluorenol-based cyclophanes exhibited high fluorescence quantum yields, which were significantly higher than that of an acyclic reference molecule (78–82 % vs. 48 %). The bending effect on the chiroptical property was also examined, which revealed that the anisotropy factors (gabs values) for electronic circular dichroism (ECD) of these 9-fluorenol-based planar chiral bent cyclophanes increase as the tether length becomes shorter. 相似文献
36.
Treatment of a meso‐diarylporphyrin with PhI(OAc)2 in the presence of BF3 ? OEt2 and propionic acid affords the corresponding porphyrinquinone in a high yield (91%). A novel quinone derived from meso‐meso β–β doubly‐fused diporphyrin was obtained as the sole byproduct (16% yield), which exhibits strong panchromatic absorption between 300 and 1000 nm. It has a low HOMO‐LUMO gap owing to expanded and low‐symmetry π‐planes. 相似文献
37.
38.
We consider preconditioned Krylov subspace iteration methods, e.g., CG, LSQR and GMRES, for the solution of large sparse least-squares problems min ∥Ax – b ∥2, with A ∈ R m×n, based on the Krylov subspaces Kk (BA, Br) and Kk (AB, r), respectively, where B ∈ R n×m is the preconditioning matrix. More concretely, we propose and implement a class of incomplete QR factorization preconditioners based on the Givens rotations and analyze in detail the efficiency and robustness of the correspondingly preconditioned Krylov subspace iteration methods. A number of numerical experiments are used to further examine their numerical behaviour. It is shown that for both overdetermined and underdetermined least-squares problems, the preconditioned GMRES methods are the best for large, sparse and ill-conditioned matrices in terms of both CPU time and iteration step. Also, comparisons with the diagonal scaling and the RIF preconditioners are given to show the superiority of the newly-proposed GMRES-type methods. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
39.
Christine Gregory Ken Darby-DowmanGautam Mitra 《European Journal of Operational Research》2011,212(2):417-428
Robust optimization is a tractable alternative to stochastic programming particularly suited for problems in which parameter values are unknown, variable and their distributions are uncertain. We evaluate the cost of robustness for the robust counterpart to the maximum return portfolio optimization problem. The uncertainty of asset returns is modelled by polyhedral uncertainty sets as opposed to the earlier proposed ellipsoidal sets. We derive the robust model from a min-regret perspective and examine the properties of robust models with respect to portfolio composition. We investigate the effect of different definitions of the bounds on the uncertainty sets and show that robust models yield well diversified portfolios, in terms of the number of assets and asset weights. 相似文献
40.
Abachi S Derrick M Kooijman P Musgrave B Price LE Repond J Sugano K Blockus D Brabson B Brom J Jung C Ogren H Rust DR Akerlof C Chapman J Errede D Ken MT Meyer DI Neal H Nitz D Thun R Tschirhart R Baringer P Bylsma BG DeBonte R Koltick D Low EH McIlwain RL Miller DH Ng CR Shibata EI 《Physical review D: Particles and fields》1989,40(3):902-905