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151.
The conformational (cis and trans) stability and electronic structures of (C(60)CHCOO)(2)-Sn(IV) porphyrin, recently synthesized as a novel fullerene-porphyrin-fullerene triad linked by metal axial coordination, have been studied by ab initio calculations. The cis conformer was found to be slightly more stable than the trans by 1.38 kcal/mol in the neutral compound. Upon the addition of an electron to the triad, the relative stability of the cis conformer was found to be higher (3.29 kcal/mol) than that in the neutral one. From the investigation of frontier molecular orbitals, for the cis conformer, it was found that the electrons are localized in HOMO of the porphyrin, while the electrons are localized in LUMO of the syn-fullerene. For the trans conformer, it was found that the electrons are localized in HOMO of the porphyrin, while the electrons are localized in LUMO of one of the two fullerene moieties, and the electrons are localized in LUMO2 of the other fullerene moiety, but the LUMO and LUMO2 have the same orbital energy. Thus, the PET may take place unidirectionally in the cis conformer from the porphyrin to the syn-fullerene, while it is bidirectional from the porphyrin to both of the fullerene moieties. 相似文献
152.
Chul‐Kyu Lee Se Yeob Park Hong Yoon Jung Chang‐Kyu Lee Byeong‐Geun Son Hyo Jin Kim Young‐Joo Lee Young‐Chang Joo Jae Kyeong Jeong 《固体物理学:研究快报》2013,7(3):196-198
Zn–Sn–O (ZTO) thin film transistors (TFTs) were fabricated with a Cu source/drain electrode. Although a reasonably high mobility (μFE) of 13.2 cm2/Vs was obtained for the ZTO TFTs, the subthreshold gate swing (SS) and threshold voltage (Vth) of 1.1 V/decade and 9.1 V, respectively, were inferior. However, ZTO TFTs with Ta film inserted as a diffusion barrier, exhibited improved SS and Vth values of 0.48 V/decade and 3.0 V, respectively as well as a high μFE value of 18.7 cm2/Vs. The improvement in the Ta‐inserted device was attributed to the suppression of Cu lateral diffusion into the ZTO channel region. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
153.
Nanoparticles of a three-dimensional coordination polymer, [Pb(L)(μ2-Br)(H2O)]n (1), (L? = 1H-1,2,4-triazole-3-carboxylate), have been synthesized by an ultrasonic method and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The thermal stability of compound 1 both its bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal (DTA) analyses and compared each other. Concentration of initial reagents effects and the role of power ultrasound irradiation on size and morphology of nano-structured compound 1, have been studied. Calcination of the compound 1 at 500 °C under air atmosphere yields Pb3O2Br2 nanoparticles. 相似文献
154.
The determination of the equation of state (EOS) of amorphous materials is very important for fundamental understanding of the glass transition and applications as well. Simultaneous observation of both longitudinal and transverse acoustic modes by Brillouin scattering spectroscopy has been one of the major methods to obtain EOS of amorphous materials. However, the transverse acoustic mode is hardly seen from some of the amorphous polymers, which makes it difficult to derive EOS. The temperature and pressure dependences of the acoustic properties of amorphous ethylene–vinyl acetate (EVA) copolymer were measured by using high-pressure Brillouin scattering spectroscopy. The temperature variation induced large changes in the frequency shift and linewidth of the longitudinal acoustic mode due to strong coupling between the structural relaxation process and the propagating density fluctuations. The residual linewidth in the glassy state was attributed to the remnant intramolecular motions of EVA, the activation energy of which was estimated to be ~3.30 ± 0.27 kcal/mol. The pressure–density relationship of EVA could be obtained for the first time by measuring the refractive index and using the Lorentz–Lorenz equation. The density and the refractive index exhibited monotonic increase up to approximately 12 GPa. The strong reduction of the acoustic damping at low pressures below ~3 GPa was attributed to the collapsing free volume in EVA. The present study clearly shows that measuring the refractive index by high-pressure Brillouin spectroscopy may be an alternative method to get the EOS of polymeric materials whose transverse acoustic mode is too weak to be observed. 相似文献
155.
A sensitive explosive was coated with a less sensitive explosive in order to improve stability while maintaining explosion performance. Agglomeration of 3‐nitro‐1,2,4‐triazole‐5‐one (NTO) on the surface of cyclotetramethylene tetranitramine (HMX) crystals in water‐N ‐methyl‐2‐pyrrolidone (NMP) solvent was performed by cooling crystallization. Phenomena for coating by crystallization and agglomeration were studied by in‐situ measurement. The agglomeration kinetic for the coating of NTO on HMX crystals was correlated with the 3rd power of the solution supersaturation and the 2nd power of the number of the suspended particles. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
156.
Electrochemical oxidative radical sulfonylation/semipinacol rearrangement sequences of alkenylcyclobutanols have been developed. The reaction proceeds in an undivided electrochemical cell equipped with platinum plate electrodes employing sodium iodide as a redox catalyst and a supporting electrolyte. This approach is environmentally benign by using shelf-stable arylsulfonyl hydrazides as arylsulfonyl radical precursor and electrons as oxidizing reagents. The present protocol offers a facile way to prepare β-sulfonated cyclic ketone derivatives. 相似文献
157.
Sanghan Lee Wooyoung Jin Su Hwan Kim Se Hun Joo Gyutae Nam Pilgun Oh Young‐Ki Kim Sang Kyu Kwak Jaephil Cho 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(31):10588-10595
Oxygen vacancies (OV) are native defects in transition metal (TM) oxides and their presence has a critical effect on the physicochemical properties of the oxide. Metal oxides are commonly used in lithium‐ion battery (LIB) cathodes and there is still a lack of understanding of the role of OVs in LIB research field. Here, we report on the behavior of OVs in a single‐crystal LIB cathode during the non‐equilibrium states of charge and discharge. We found that microcrack evolution in a single crystal occurs due to OV condensation in specific crystallographic orientations generated by the continuous migration of OVs and TM ions. Moreover, understanding the effects of the presence and diffusion of OVs in metal oxides enables the elucidation of most of the conventional mechanisms of capacity fading in LIBs and provides new insights for new electrochemical applications. 相似文献
158.
Mykola Telychko Jie Su Aurelio Gallardo Yanwei Gu Jesús I. Mendieta‐Moreno Dongchen Qi Anton Tadich Shaotang Song Pin Lyu Zhizhan Qiu Hanyan Fang Ming Joo Koh Jishan Wu Pavel Jelínek Jiong Lu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(51):18764-18770
The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution‐ and solid‐phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom‐up on‐surface synthesis of well‐defined nanostructures. We report an internal strain‐induced skeletal rearrangement of one‐dimensional (1D) metal–organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu‐catalyzed debromination of organic monomers to generate 1,5‐dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond‐resolved non‐contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate‐induced internal strain drives the skeletal rearrangement of MOCs via 1,3‐H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain‐induced structural rearrangement in 1D systems will enrich the toolbox for on‐surface synthesis of novel functional materials and quantum nanostructures. 相似文献
159.
Silver coated ZnO nanorods and nanoflakes with different crystallographic orientations were synthesized by a combination of sputter deposition and solution growth process. Catalytic properties of morphology‐dependent Ag/ZnO nanostructures were then investigated for urea sensors without enzyme. Ag/ZnO nanorods on carbon electrodes exhibit a higher catalytic activity and an improved efficiency than Ag/ZnO nanoflakes on carbon electrodes. Ag/ZnO nanorod catalysts with more electrochemically surface area (169 cm2 mg?1) on carbon electrode facilitate urea electrooxidation due to easier electron transfer, which further promotes the urea electrolysis. The Ag/ZnO nanorod catalysts also show a significant reduction in the onset voltage (0.410 V vs. Ag/AgCl) and an increase in the current density (12.0 mA cm?2 mg?1) at 0.55 V vs Ag/AgCl. The results on urea electrooxidation show that Ag/ZnO nanostructures can be a potential catalyst for non‐enzymatic biosensors and fuel cells. 相似文献
160.
Genlin Sun Jeong Soo Kim Yune Sung Kim Hyun Joo An Won Jo Cheong 《Journal of separation science》2019,42(16):2612-2620
A stationary phase was prepared by chemical derivatization of the support particles with a layer of copolymer composed of styrene and N‐phenyl acrylamide. Silica monolith particles of ca. 2.6 µm (volume‐based average) have been prepared as the support particles by sol‐gel reaction followed by differential sedimentation. The particles were reacted with 3‐chloropropyl trimethoxysilane followed by sodium diethyldithiocarbamate to introduce an initiator moiety. Then, the copolymer layer was immobilized via reversible addition‐fragmentation transfer polymerization. The resultant phase was packed in glass‐lined stainless‐steel micro‐columns (1 x 150 mm) and evaluated for the separation of a mixture composed of five peptides (Trp‐Gly, Thr‐Tyr‐Ser, angiotensin I, isotocin and bradykinin). The effect of monomer mixing ratio (styrene versus N‐phenyl acrylamide) on the chromatographic separation efficiency of the stationary phase was examined. A number of theoretical plates (N) as high as 33 600 plates/column (224 000 plates/m, 4.46 µm plate height) was achieved using the column packed with the optimized stationary phase. The column‐to‐column reproducibility based on three columns packed with three different batches of stationary phase was found satisfactory in separation efficiency, retention factor, and asymmetry factor. 相似文献