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41.
目前临床诊断中钆基造影剂的应用十分广泛,然而其对人体的毒性无法忽视,因此研究者致力于低毒性造影剂的研发。氧化铁纳米颗粒(Iron Oxide Nanoparticles,IONP)因其超顺磁性在磁共振成像(Magnetic Resonance Imaging,MRI)中具有良好的暗对比效果,并且具有良好的生物相容性。随着生物材料和分子影像技术的发展,IONP在MRI成像中的应用愈发广泛。近年来,IONP在多模态成像和诊断治疗一体化方面取得了进展。本文将以IONP的MRI成像机理、制备和表面修饰为基础,阐述近年来IONP在MRI成像应用的研究成果和问题,期望IONP取得更好的发展。 相似文献
42.
针对Ni单原子催化剂表面的CO2电还原反应(CO2RR), 提出了以Ni为活性位点的“单中心”机理以及同时借助Ni位点还原和碳氮锚定位水解的“双功能”机理. 依据稳态极化的实验结果, 开展了CO2RR的动力学解析与模型参数的敏感性分析; 借助暂态模型方程, 分别获取可表达CO2RR线性与非线性频响特征的电化学阻抗谱(EIS)与总谐波失真(THD)谱. 研究结果表明, CO2的溶解分压对CO2RR活性影响最显著. 若CO2RR遵循“单中心”机理, Ni位点COOHads的形成为速率控制步骤; 但若为“双功能”机理, 碳氮锚定位的水解与Ni位点的CO2,ads还原同为速率控制步骤. EIS理论上可用于区分CO2RR的“单中心”机理与“双功能”机理; 与之相比, THD谱在CO2RR的机理识别中并无优势. 相似文献
43.
Jianxin Guan Rong Wei Antonio Prlj Jie Peng Kun-Han Lin Jitian Liu Han Han Prof. Clémence Corminboeuf Prof. Dahui Zhao Prof. Zhihao Yu Prof. Junrong Zheng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):15013-15019
The mechanism of aggregation-induced emission, which overcomes the common aggregation-caused quenching problem in organic optoelectronics, is revealed by monitoring the real time structural evolution and dynamics of electronic excited state with frequency and polarization resolved ultrafast UV/IR spectroscopy and theoretical calculations. The formation of Woodward–Hoffmann cyclic intermediates upon ultraviolet excitation is observed in dilute solutions of tetraphenylethylene and its derivatives but not in their respective solid. The ultrafast cyclization provides an efficient nonradiative relaxation pathway through crossing a conical intersection. Without such a reaction mechanism, the electronic excitation is preserved in the molecular solids and the molecule fluoresces efficiently, aided by the very slow intermolecular charge and energy transfers due to the well separated molecular packing arrangement. The mechanisms can be general for tuning the properties of chromophores in different phases for various important applications. 相似文献
44.
De-Hui Guan Xiao-Xue Wang Ma-Lin Li Fei Li Li-Jun Zheng Prof. Xiao-Lei Huang Prof. Ji-Jing Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19686-19692
A photoinduced flexible Li-CO2 battery with well-designed, hierarchical porous, and free-standing In2S3@CNT/SS (ICS) as a bifunctional photoelectrode to accelerate both the CO2 reduction and evolution reactions (CDRR and CDER) is presented. The photoinduced Li-CO2 battery achieved a record-high discharge voltage of 3.14 V, surpassing the thermodynamic limit of 2.80 V, and an ultra-low charge voltage of 3.20 V, achieving a round trip efficiency of 98.1 %, which is the highest value ever reported (<80 %) so far. These excellent properties can be ascribed to the hierarchical porous and free-standing structure of ICS, as well as the key role of photogenerated electrons and holes during discharging and charging processes. A mechanism is proposed for pre-activating CO2 by reducing In3+ to In+ under light illumination. The mechanism of the bifunctional light-assisted process provides insight into photoinduced Li-CO2 batteries and contributes to resolving the major setbacks of the system. 相似文献
45.
Xinfeng Zhu Yanli Mao Hongpan Liu Haiyan Kang Biao Liu Zhongxian Song Xueping Liu Yifei Guo Huixian Du Qiulin Zhang 《应用有机金属化学》2020,34(2):e5285
FeOx, TiO2, and Fe–Ti–Ox catalysts were synthesized and used in the catalytic hydrolysis of hydrogen cyanide (HCN). Nearly 100% HCN conversion was achieved at 250 °C over the Fe–Ti–Ox catalyst. TiO2 rutile was detected over TiO2, but not over Fe–Ti–Ox, which suggested that the interaction between Fe and Ti species could inhibit the TiO2 phase transition. Furthermore, the interaction between Fe and Ti species over Fe–Ti–Ox could promote the selectivity of NH3 and CO. The mechanism of hydrolysis of HCN over FeOx, TiO2, and Fe–Ti–Ox can be given as follows: HCN + H2O → methanamide → ammonium formate → formic acid → H2O + CO. 相似文献
46.
Alpha-phenylethanol (PE) is an essential chemical in the field of medicine and synthetic perfumery. Therefore, in this work, we used a supported Ni–B–P amorphous alloy catalyst (Ni–B–P/SiO2) in the hydrogenation of acetophenone (AP) to α-PE, which demonstrated excellent catalytic activity and selectivity, compared with Ni–B/SiO2 (KBH4 reduction of nickel salt). Ni–B–P/SiO2 exhibited a high AP hydrogenation conversion of approximately 99%, whereas the PE selectivity reached up to 94%, which is approximately 1.4-fold higher than that of Ni–B/SiO2 (about 69%), thereby directly proving the unique inhibition of AP hydrogenation over hydrogenation of P in the Ni–B catalytic system. The doped P in Ni–B–P/SiO2 enhances the oxidation resistance and maintains the valence stability of Ni and B. Furthermore, sufficient experimental data were collected to determine the kinetic parameters. Based on the Langmuir–Hinshelwood model, we assumed that (i) AP and H2 compete for adsorption on Ni–B–P/SiO2; (ii) AP has strong adsorptive capacity on Ni–B–P/SiO2; and (iii) PE coverage on the catalyst was negligible. Then, the dynamic equation was derived, which indicated that experimental data agree well with the dynamic model. Finally, the activation energy was confirmed to be 50.73 KJ/mol. This report will open up an avenue for the industrialization of amorphous alloy catalysts. 相似文献
47.
48.
Weiyi Li Geng Leng Caiqin Li Yajing Lyu 《International journal of quantum chemistry》2020,120(8):e26150
The mechanisms of CO2 coupling with the propargylic alcohol using alkali carbonates M2CO3 (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs2CO3-mediated carboxylative cyclization of the propargylic alcohol with CO2, and (b) the conversion of the αACC intermediate with Cs2CO3 to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO3 together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO2 with the propargylic alcohol. Compared to other alkali carbonates M2CO3 (M = Li, Na, K), the stronger basicity of Cs2CO3 and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield. 相似文献
49.
The insertion of an alkyne into transition metal–hydrogen bonds is a key elementary step in catalytic polymerization and hydrogenation processes. It was found that a (Z)- or (E)-type alkyenyl complex can be formed through trans/cis stereospecific processes. In this work, the reaction mechanism of Cp2M(L)H [Cp = η5-C5H5; M = Nb, V; L = CO, P (OMe)3] with dimethylacetylene dicarboxylate (DMAD), and the factors influencing the stereoselectivity have been investigated based on density functional theory calculations. The calculated results show that all of the reactions are exothermic. For L = CO, the Z-isomer product forms first even at low temperatures because of the low Gibbs free energy barrier (ΔG#). Then the Z-pro converts to E-pro , while for L = P (OMe)3, the exclusive product is the E-isomer. For different metal centers, the reaction mechanisms of the Cp2M(CO)H + DMAD (M = Nb and V) reaction are similar, while their products are different at room temperature. For M = Nb, because the energy barrier of the isomerization from Z-pro to E-pro is low and the relative free energies of Z-pro and E-pro are almost equal, both Z-pro and E-pro can be obtained. While for the Cp2V(CO)H + DMAD reaction, only the Z-pro can be obtained under mild conditions, E-pro can be obtained only at high temperatures. For the Cp2M(CO)H+DMAD(M=V and Nb) reactions, the formation of E-isomer products proceeds via two five-membered ring transition states. The calculated results provide an reasonable explanation for the experimental results and predict a new insertion reaction. 相似文献
50.
Newly established in 2018, the UK Research and Innovation (UKRI) strengthens the strategic coordination of the UK research and innovation system by bringing together seven Research Councils, Research England, and Innovate UK. Through its nine organizations, UKRI funds multidisciplinary and interdisciplinary research in a number of priority areas. It also runs the Strategic Priorities Fund to support multidisciplinary and interdisciplinary research in strategic areas identified by government policies as well as the Global Challenges Research Fund to promote challenge-led interdisciplinary research needed by developing countries. The UKRI makes significant efforts to engage stakeholders in the development, design, and implementation of multidisciplinary and interdisciplinary programs. It has also developed a range of mechanisms to improve the evaluation of multidisciplinary and interdisciplinary projects. Chinese science and innovation funding agencies could draw upon the UKRI experience from four aspects to advance interdisciplinary research in China. 相似文献