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61.
The Effect of Metal‐Ligand Affinity on Fe3O4_Supported Co–Rh Catalysts for Dicyclopentadiene Hydroformylation 下载免费PDF全文
Yubo Ma Shaojun Qing Nana Li Letao Zhang Shouzhu Li Zhixian Gao Hongyi Li Wumanjiang Eli Tianfu Wang 《国际化学动力学杂志》2015,47(10):621-628
The catalytic performances of Co‐Rh/Fe3O4 catalysts modified with phosphine ligands (PPh3) and its analogues on dicyclopentadiene hydroformylation were evaluated. Among these catalysts, Co‐Rh/Fe3O4 modified with tris(p‐trifluoromethylphenyl)phosphine was determined to be effective for monoformyltricyclodecanes production, whereas Co‐Rh/Fe3O4 modified with PPh3 or tri‐p‐tolylphosphine was effective for the diformyltricyclodecanes production. To investigate the ligand effects, the complex catalyst system (Co‐Rh/Fe3O4 and phosphine ligand) was subjected to pretreatment with syngas and then characterized by thermogravimetry and differential thermal analysis (TG‐DTA). It was determined that the threshold decomposition temperature reflected the corresponding Rh‐phosphine interaction strength, affecting the catalytic selectivity toward different products. A weak Rh‐phosphine interaction was desirable to produce monoformyltricyclodecanes with fast reaction kinetics, whereas a strong Rh‐phosphine complex was required for the synthesis of diformyltricyclodecanes. In addition to the selectivity rule shown in the PPh3 series, experiments with other ligands also demonstrated similar selectivity trends. 相似文献
62.
Back Cover: Ligand Symmetry Modulation for Designing a Mesoporous Metal–Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization (Chem. Eur. J. 27/2015) 下载免费PDF全文
63.
A novel tiled Ti:sapphire(Ti:S)amplifier was experimentally demonstrated with>1 J amplified chirped pulse output.Two Ti:S crystals having dimensions of 14 mm×14 mm×25 mm were tiled as the gain medium in a four-pass amplifier.Maximum output energy of 1.18 J was obtained with 2.75 J pump energy.The energy conversion efficiency of the tiled Ti:S amplifier was comparable with a single Ti:S amplifier.The laser pulse having the maximum peak power of 28 TW was obtained after the compressor.Moreover,the influence of the beam gap on the far field was discussed.This novel tiled Ti:S amplifier technique can provide a potential way for 100 PW or EW lasers in the future. 相似文献
64.
Qing Liu Yibin Liu Hua Zheng Chunmei Li Yi Zhang Qiuyu Zhang 《Journal of polymer science. Part A, Polymer chemistry》2020,58(8):1092-1104
Thermoset polymer elastomers that are capable of autonomous repairability upon physical damage at ambient temperature are highly desirable because of their thermal and environmental resistance, outstanding mechanical toughness and stability. To aim at this goal, we demonstrated that tris(diethylamino)phosphine was initially proven as an efficient catalyst for the aliphatic disulfide exchange at mild condition. By making use of the aliphatic disulfide bond reshuffling and elasticity of polyurethane elastomers, the inherently cross-linked polysulfide-based poly(thiourethane-urethane) elastomers were prepared and exhibited the ability to mend without extrinsic stimuli in the presence of phosphorus catalyst at room temperature after artificially damaged. The self-healing efficiency via the mechanical recovery approach was investigated to be mainly dependent upon the cross-linking density of polysulfide and hard segments chemistry, which in turns determined the molecular chain diffusion and reshuffling that was corroborated by the stress-relaxation study. The thermoset elastomer based on asymmetric diisocynate showed a maximum self-healing efficiency of 85.6% compared to 71.6% for the elastomer with symmetric monomer building blocks. The self-healable polymer was confirmed to be recyclable and reprocessable through a cut-compression processing cycle under a quite mild pressure and temperature thanks to the disulfide bond reshuffling. Meanwhile, the recycled thermoset elastomer well maintained the mechanical properties to its original material. 相似文献
65.
Bo Wang Dr. Wencheng Du Dr. Yang Yang Dr. Yufei Zhang Dr. Qi Zhang Prof. Xianhong Rui Dr. Hongbo Geng Prof. Cheng Chao Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(29):6554-6560
Lithium ion batteries (LIBs) at present still suffer from low rate capability and poor cycle life during fast ion insertion/extraction processes. Searching for high-capacity and stable anode materials is still an ongoing challenge. Herein, a facile strategy for the synthesis of ultrathin GeS2 nanosheets with the thickness of 1.1 nm is reported. When used as anodes for LIBs, the two-dimensional (2D) structure can effectively increase the electrode/electrolyte interface area, facilitate the ion transport, and buffer the volume expansion. Benefiting from these merits, the as-synthesized GeS2 nanosheets deliver high specific capacity (1335 mAh g−1 at 0.15 A g−1), extraordinary rate performance (337 mAh g−1 at 15 A g−1) and stable cycling performance (974 mAh g−1 after 200 cycles at 0.5 A g−1). Importantly, our fabricated Li-ion full cells manifest an impressive specific capacity of 577 mAh g−1 after 50 cycles at 0.1 A g−1 and a high energy density of 361 Wh kg−1 at a power density of 346 W kg−1. Furthermore, the electrochemical reaction mechanism is investigated by the means of ex-situ high-resolution transmission electron microscopy. These results suggest that GeS2 can use to be an alternative anode material and encourage more efforts to develop other high-performance LIBs anodes. 相似文献
66.
Manman Liu Yang Zhu Tiantian Wu Dr. Junjie Cheng Prof. Yangzhong Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(33):7442-7450
Ferritin is an iron-storage protein nanocage that is assembled from 24 subunits. The hollow cavity of ferritin enables its encapsulation of various therapeutic agents; therefore, ferritin has been intensively investigated for drug delivery. The use of antibody-ferritin conjugates provides an effective approach for targeted drug delivery. However, the complicated preparation and limited protein stability hamper wide applications of this system. Herein, we designed a novel nanobody-ferritin platform (Nb-Ftn) for targeted drug delivery. The site-specific conjugation between nanobody and ferritin is achieved by transglutaminase-catalyzed protein ligation. This ligation strategy allows the Nb conjugation after drug loading in ferritin, which avoids deactivation of the nanobody under the harsh pH environment required for drug encapsulation. To verify the tumor targeting of this Nb-Ftn platform, a photodynamic reagent, manganese phthalocyanine (MnPc), was loaded into the ferritin cavity, and an anti-EGFR nanobody was conjugated to the surface of the ferritin. The ferritin nanocage can encapsulate about 82 MnPc molecules. This MnPc@Nb-Ftn conjugate can be efficiently internalized by EGFR positive A431 cancer cells, but not by EGFR negative MCF-7 cells. Upon 730 nm laser irradiation, MnPc@Nb-Ftn selectively killed EGFR positive A431 cells by generating reactive oxygen species (ROS), whereas no obvious damage was observed on MCF-7 cells. Given that ferritin can be used for encapsulation of various therapeutic agents, this work provides a strategy for facile construction of nanobody-ferritin for targeted drug delivery. 相似文献
67.
Dr. Ruofei Cheng Prof. Dr. Zaozao Qiu Prof. Dr. Zuowei Xie 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7212-7218
Iridium-catalyzed formal alkyne hydroboration with cage B−H of o-carborane has been achieved, leading to the controlled synthesis of a series of 3,6-[trans-(AlkCH=CH)]2-o-carboranes (Alk=alkyl), 3-cis-(ArCH=CH)-o-carboranes (Ar=aryl), and 3-cis-(ArCH=CH)-6-trans-(AlkCH=CH)-o-carboranes in high yields with excellent regio- and very good cis–trans selectivity. The most electron-deficient B(3,6)−H vertices favor oxidative addition on electron-rich metal centers, which is responsible for the regioselectivity. On the other hand, the configuration of the resultant olefinic units is dominated by alkyne substituents. Alkyl groups lead to a trans-configuration whereas bulky aryl substitutions result in cis-configuration. 相似文献
68.
Wenxiang Liu Lele Lu Qiang Li Boyuan Wu Ruizhe Zhang Wei Shi Peng Cheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(53):12206-12211
Photocatalytic hydrogen evolution by water splitting is highly important for the application of hydrogen energy and the replacement of fossil fuel by solar energy, which needs the development of efficient catalysts with long-term catalytic stability under light irradiation in aqueous solution. Herein, Zn0.5Cd0.5S solid solution was synthesized by a metal–organic framework-templated strategy and then loaded with MoS2 by a hydrothermal method to fabricate a MoS2/Zn0.5Cd0.5S heterojunction for photocatalytic hydrogen evolution. The composition of MoS2/Zn0.5Cd0.5S was fine-tuned to obtain the optimized 5 wt % MoS2/Zn0.5Cd0.5S heterojunction, which showed a superior hydrogen evolution rate of 23.80 mmol h−1 g−1 and steady photocatalytic stability over 25 h. The photocatalytic performance is due to the appropriate composition and the formation of an intimate interface between MoS2 and Zn0.5Cd0.5S, which endows the photocatalyst with high light-harvesting ability and effective separation of photogenerated carriers. 相似文献
69.
Dr. Jinghui Zhang Lei Gong Xiaoshuang Zhang Dr. Mengliang Zhu Chaorui Su Qing Ma Dr. Dongdong Qi Prof. Yongzhong Bian Prof. Hongwu Du Prof. Jianzhuang Jiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(61):13842-13848
Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP) n (n=1–3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40–0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δTPA values of TAT-(ZnP)2 and TAT-(ZnP)3 further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D -π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D -π-A-D multipolar array. 相似文献
70.
Dr. Wei Zheng Xiao-Lei Yang Dr. Gui-Yuan Wu Prof. Lin Cheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11695-11700
In this work, well-defined two-dimensional metallacycles have been successfully employed for the well-controlled self-assembly of gold nanoparticles (AuNPs) into discrete clusters such as dimers, trimers, tetramers, pentamers and even hexamers at the water–oil interface for the first time. Furthermore, the modular construction of metallacycle molecules allows precise control of spacing between the gold nanoparticles. Interestingly, it was found that interparticle spacing below 5 nm created by molecular metallacycles in the resultant discrete gold nanoparticle clusters led to a strong plasmon coupling, thus inducing great field enhancement inside the gap between the NPs. More importantly, different discrete clusters with precise interparticle spacing provide a well-defined system for studying the hot-spot phenomenon in surface-enhanced Raman scattering (SERS); this revealed that the SERS effects were closely related to the interparticle spacing. 相似文献