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991.
Yoshiki Fujita Hiroshi Ota Tomohiro Matsushita Takayuki Muro Yasunori Senba Fumihiko Matsui 《Surface and interface analysis : SIA》2019,51(1):74-78
A series of C 1s photoelectron intensity angular distribution (PIAD) patterns from a crystalline graphite surface were mapped in two dimensions at intervals of 20 μm. Two kinds of PIAD patterns rotated by 30° from each other, corresponding to the two domains from the twinned crystal, were found. The standard deviation of the diffraction contrast was evaluated for each PIAD pattern from its intensity histogram. Surprisingly, we found that odd-number- (most probably single-) atom-height steps on the flat terrace region and their local atomic arrangement can be identified by two-dimensionally mapping the standard deviation values. Furthermore, we analyzed the photoelectron diffraction patterns and noticed that the normal direction of the sample surface at each point was slightly inclined differently. By connecting all the inclination angle data, the micrometer-scale corrugation of the sample surface was successfully visualized. Scanning photoelectron diffraction microscopy has been shown to be useful for the nanometer- and micrometer-scale structural imaging. 相似文献
992.
Yusuke Ueda Dr. Tomohiro Iwai Prof. Dr. Masaya Sawamura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(40):9410-9414
The hydroacylation of vinylarenes with acyl fluorides and hydrosilanes was enabled by a synergistic bimetallic Ni/Cu-catalytic system, giving access to the corresponding branched ketone products. The reaction takes place under mild conditions at 25–80 °C and tolerates base-sensitive functional groups such as methoxycarbonyl and acetoxy groups. 相似文献
993.
Takashi Noda Yuya Doi Yutaka Ohta Shin-ichi Takata Atsushi Takano Yushu Matsushita 《Journal of polymer science. Part A, Polymer chemistry》2020,58(15):2098-2107
A four-branched cage-shaped poly(ethylene oxide) (4C-PEO) was prepared by a coupling reaction at very dilute condition between two kinds of end-functional four-armed star-shaped PEOs having amino and N-hydroxysuccinimide groups on their four ends, followed by purification using α-cyclodextrin (α-CD). The raw coupling reaction product shows multiple peaks including various high molecular weight multimeric products in size-exclusion chromatography measurements, while the product after α-CD purification shows a single peak eluted slightly earlier than the precursor star PEOs. Moreover, the final product obtained has about twice higher molecular weight than the star precursors. These results suggest that the targeted 4C-PEO polymer was successfully isolated through the α-CD purification. Small-angle neutron scattering (SANS) measurements of the final product in dilute solution were conducted, and its chain conformation was evaluated from the scattering profile in comparison with linear and star polymers. It has been found that the cage-shaped sample exhibits a distinct peak at lower q-region in the Kratky plot, which is in strong contrast with the linear counterpart. This result must be originated from the characteristic cage-shaped architecture, that is, having branched and closed-loop configurations, and hence having higher segmental density than simple linear and star molecules. In fact, the present experimental result is consistent with the recent Monte Carlo simulation reported by Uehara and Deguchi. 相似文献
994.
A carbon nanotube (CNT)‐modified electrode was fabricated by dropping a dispersion of multi‐walled CNTs in water‐soluble and amphiphilic phospholipid polymer with both dispersing ability and anti‐biofouling property onto a Au electrode. A poly(2‐methacryloyloxyethyl phosphorylcholine‐co‐n‐butyl methacrylate) (PMB) composed from 50 mol% of 2‐methacryloxylethyl phosphorylcholine and 50 mol% of n‐butyl methacrylate (PMB50) was used as dispersing reagent for CNTs. The dispersion of water‐insoluble material by PMB50 and its antifouling effects in electrochemical analysis were investigated. The CNT‐modified electrode showed an anodic peak potential that was shifted negatively and an increase in the current value for the electrolytic oxidation of nicotinamide adenine dinucleotide. In addition, the charge on PMB50 did not inhibit the electrochemical reaction of the redox compounds K3[Fe(CN)6], [Ru(NH3)6]Cl3, and hydroxymethylferrocene. Cyclic voltammetry of K3[Fe(CN)6] in 4 % bovine serum albumin (BSA) using a bare Au electrode, the anodic peak current was reduced to 47 % of that without BSA. In contrast, the antifouling effect of the PMB50‐coated electrode meant that the current was only reduced to 70 % of that without BSA. 相似文献
995.
Natsuhiro Azuma Fumio Sanda Toshikazu Takata Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1997,35(6):1007-1012
Cationic copolymerization of seven-membered cyclic sulfite, 1,3,2-dioxathiepane-2-oxide (1) and oxetane (2) in one-shot feeding was carried out to obtain the corresponding copolymer. When a mixture of equimolar amount of 1 and 2 reacted at 0°C in the presence of methyl trifluoromethanesulfonate (T fOMe) as a cationic initiator, T fOMe and 2 were completely consumed without the consumption of 1. After rising the polymerization temperature up to 25°C, 1 started to be consumed to obtain the corresponding copolymer of 1 and 2. The obtained copolymer showed a unimodal GPC curve, and it afforded a polyether showing a unimodal GPC after alkaline hydrolysis. These results strongly suggested the occurrence of the block copolymerization in one-shot feeding. From the molecular orbital examination, the formation of block copolymerization in one-shot feeding was discussed to be caused by the much larger polymerizability of 2 than that of 1. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1007–1012, 1997 相似文献
996.
Synthesis of a Structure‐Definite α‐Cyclodextrin‐Based Macromolecular [3]Rotaxane Using a Size‐Complementary Method 下载免费PDF全文
Dr. Yosuke Akae Dr. Hiromitsu Sogawa Prof. Toshikazu Takata 《Angewandte Chemie (International ed. in English)》2018,57(36):11742-11746
The challenging synthesis of an α‐cyclodextrin (CD)‐based macromolecular rotaxane with definite structure was fulfilled using a size‐complementary method. A new peracetylated (PAc) α‐CD‐based size‐complementary [3]rotaxane was prepared and its thermal dissociation kinetics studied. The de‐slippage mechanism was found to be different from that of the native α‐CD‐based system. PAcα‐CD‐based size‐complementary [3]rotaxanes were employed as initiators for a ring‐opening polymerization of ?‐caprolactone to obtain the macromolecular [3]rotaxanes. Detailed investigation of component dissociation showed the highly movable character of the wheel on the polymer main chain. A general method for controlling the movement of wheels in rotaxane frameworks, even in polymer systems, was established. This will enable the development of new supramolecular architectures and molecular machines. 相似文献
997.
Atsushi Kikkawa Toshikazu Takata Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1991,29(8):1089-1095
The effect of alkyl substituents on cationic polymerization of styrene with p-methoxybenzyldialkysulfonium salts was studied. p-Methoxybenzyl tetramethylene ( 1 ), dimethyl ( 2 ), diethyl ( 3 ), dibuty ( 4 ), and diisopropylsulfonium salts ( 5 ) were synthesized by the reaction of p-methoxybenzyl bromide with the corresponding sulfides, followed by exchange of the counter anion Br? with SbF?6. These sulfonium salts served as potent cationic thermal initiators of which activity was estimated by the bulk and solution polymerizations of styrene. The bulk polymerizations with 1–4 (0.1 mol %) for 30 min gradually proceeded at 30–50°C, but the exothermic polymerization occurred vigorously at 40–60°C. The Polymerization with 5 took place exothermically even at room temperature. Temperature-conversion curves of the polymerizations for 30 and 5 min revealed that the activity of the sulfonium salts was in the following order: 5 > 4 > 3 > 2 ≈ 1 . This order was explained by the order of the bulkiness of the alkyl substituents on the sulfur atom. Number-average molecular weight (M?n) of polystyrene obtained by the polymerization undergoing no exothermic process was in a range of 6600–16000, which depended on the structure of the alkyl substituents: the more bulky the substituent was, the higher M?n was. 相似文献
998.
Fumio Hamazu Sumio Akashi Tatsuya Koizumi Toshikazu Takata Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1991,29(13):1845-1851
Benzyl o-, m-, and p-substituted phenyl methyl sulfonium salts ( 2b – 2g ) were synthesized and their activities as cationic initiators were evaluated in the bulk polymerization of phenyl glycidyl ether (PGE). Especially, their activities were estimated with respect to the effect of substituents on the aryl groups. In the polymerizations of PGE with a series of benzyl p-substituted phenyl methyl sulfonium salts, the order of their activities was found to be 2c (CH3OCOO) > 2b (CH3COO) > 2d (CH3O) ~ 2a (HO). In particular, 2c was the most active initiator of all, capable of initiating the polymerization of PGE even at room temperature. In the polymerizations with 2a, 2e (m-Cl), 2f (o-CH3), and 2g (m-CH3), the activity of 2e was the highest of all while those of 2a, 2f , and 2g were almost the same. These results strongly suggested that the electron-withdrawing group placed on the aryl group undoubtedly enhanced the activity of the sulfonium salts as the cationic initiators. 相似文献
999.
Tsuneyuki Sato Toru Takahashi Makiko Seno Tomohiro Hirano 《Journal of polymer science. Part A, Polymer chemistry》2001,39(24):4206-4213
A combined system of sodium tetraphenylborate (STPB) and p‐chlorobenzenediazonium tetrafluoroborate (CDF) serves as an effective initiator at low temperatures for acrylate monomers such as methyl methacrylate (MMA), ethyl acrylate, and di‐2‐ethylhexyl itaconate. The polymerization of MMA with the STPB/CDF system has been kinetically investigated in acetone. The polymerization shows a low overall activation energy of 60.3 kJ/mol. The polymerization rate (Rp) at 40 °C is given by Rp = k[STPB/CDF]0.5[MMA]1.6, when the molar ratio of STPB to CDF is kept constant at unity, suggesting that STPB and CDF form a complex with a large stability constant and play an important role in initiation and that MMA participates in the initiation process. From the results of a spin trapping study, p‐chlorophenyl and phenyl radicals are presumed to be generated in the polymerization system. A plausible initiation mechanism is proposed on the basis of kinetic and electron spin resonance results. A large solvent effect on the polymerization can be observed. The largest Rp value in dimethyl sulfoxide is 11 times the smallest value in N,N‐dimethylformamide. The copolymerization of MMA and styrene with the STPB/CDF system gives results somewhat different from those of conventional radical copolymerization. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4206–4213, 2001 相似文献
1000.
Xi Yang Dr. Tomohiro Yasukawa Dr. Tei Maki Dr. Yasuhiro Yamashita Prof. Dr. Shū Kobayashi 《化学:亚洲杂志》2021,16(3):232-236
Although strong acid-treated metal oxides are useful heterogeneous superacid catalysts for various organic transformations, they usually have a limited density of acidic sites due to their low surface areas. Herein, heterogeneous trifluoromethanesulfonic acid immobilized nitrogen-doped carbon-incarcerated titanium nanoparticle (NP) catalysts have been developed that are composed of well-dispersed, small Ti NPs (ca 7 nm) that are otherwise difficult to achieve using acid-treated metal oxides. The catalysts showed high activity for Friedel–Crafts acylation with low titanium loading (2 mol%, <1 mg of metal for 1 mmol of substrate). A range of microscopic, spectroscopic and physicochemical studies revealed that the nitrogen-doped carbon immobilized the trifluoromethanesulfonic acid and that the addition of metals further changed the nature of the acidic species and enhanced catalytic activity. 相似文献