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排序方式： 共有466条查询结果，搜索用时 15 毫秒
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83.
Kadir Sentosun Marta N. Sanz Ortiz K. Joost Batenburg Luis M. Liz‐Marzán Sara Bals 《Particle & Particle Systems Characterization》2015,32(12):1063-1067
Characterization of core–shell type nanoparticles in 3D by transmission electron microscopy (TEM) can be very challenging. Especially when both heavy and light elements coexist within the same nanostructure, artifacts in the 3D reconstruction are often present. A representative example would be a particle comprising an anisotropic metallic (Au) nanoparticle coated with a (mesoporous) silica shell. To obtain a reliable 3D characterization of such an object, a dose‐efficient strategy is proposed to simultaneously acquire high‐angle annular dark‐field scanning TEM and annular dark‐field tilt series for tomography. The 3D reconstruction is further improved by applying an advanced masking and interpolation approach to the acquired data. This new methodology enables us to obtain high‐quality reconstructions from which also quantitative information can be extracted. This approach is broadly applicable to investigate hybrid core–shell materials. 相似文献
84.
van Pul C Roos FG Derksen OS Buijs J Vlaardingerbroek MT Kopinga K Wijn PF 《Magnetic resonance imaging》2004,22(9):1169-1180
In the neonatal brain, it is important to use a fast imaging technique to acquire all diffusion weighted images (DWI) for apparent diffusion coefficient (ADC) calculation. Taking into account the occurrence of typical echo planar imaging (EPI) artifacts, we have investigated whether single-shot (SSh) or multishot (MSh) DWI-EPI should be preferred. In 14 neonates, 17 adult patients and 5 adult volunteers, DWIs are obtained both with SSh and MSh EPI. The occurrence of artifacts and their influence on the ADC are explored and further quantified using simulations and phantom studies. Two radiologists scored overall image quality and diagnosability of all images. Single-shot and MSh DWI-EPI scored equally well in neonates with respect to overall image quality and diagnosability. In newborns, more motion artifacts in MSh can be noticed while N/2-ghost artifacts in SSh occur less frequently than in adults. Both N/2-ghost and motion artifacts result in significant ADC abnormalities. There is a serious risk that these artifacts will be mistaken for genuine diffusion abnormalities. N/2-ghost artifacts are hardly noticed in the neonatal brain, which might be due to smaller cerebrospinal fluid (CSF) velocity than in adults. Apparent diffusion coefficient values in MSh are unreliable if motion occurs. We conclude that for ADC calculations in neonates SSh DWI-EPI is more reliable than MSh. 相似文献
85.
Frigato T VandeVondele J Schmidt B Schütte C Jungwirth P 《The journal of physical chemistry. A》2008,112(27):6125-6133
We present a computational study of the structure and dynamics of an excess electron in a medium-sized water cluster aimed at addressing the question of interior vs exterior solvation. Ab initio Born-Oppenheimer molecular dynamics simulations were performed within the DFT framework, employing a hybrid Gaussian and plane-wave formalism together with the PBE exchange-correlation functional and norm-conserving pseudopotentials. Analysis of a 15-ps trajectory allowed us to reach the following conclusions: (i) the excess electron is predominantly located at the cluster surface (even if it is initially placed in the interior), (ii) the computed electron binding energies correlate with the electron localization rather than with its bulk vs surface location, and (iii) a dynamical interconversion between two different H-bond patterns around the electron occurs. The computed electron binding energies and the most relevant features of the IR spectrum are in a very good agreement with results of previous experimental studies. 相似文献
86.
Supramolecular bidentate phosphite ligands are presented as a new class of ligands for rhodium catalysed asymmetric hydrogenation. 相似文献
87.
Prof. Wenlin Zhang Eva J. Meeus Lei Wang Dr. Lu-Hua Zhang Shuangcheng Yang Prof. Bas de Bruin Prof. Joost N. H. Reek Dr. Fengshou Yu 《ChemSusChem》2022,15(3):e202102379
Precise regulation of the electronic states of catalytic sites through molecular engineering is highly desired to boost catalytic performance. Herein, a facile strategy was developed to synthesize efficient oxygen reduction reaction (ORR) catalysts, based on mononuclear iron phthalocyanine supported on commercially available multi-walled carbon nanotubes that contain electron-donating functional groups (FePc/CNT-R, with “R” being −NH2, −OH, or −COOH). These functional groups acted as axial ligands that coordinated to the Fe site, confirmed by X-ray photoelectron spectroscopy and synchrotron-radiation-based X-ray absorption fine structure. Experimental results showed that FePc/CNT-NH2, with the most electron-donating −NH2 axial ligand, exhibited the highest ORR activity with a positive onset potential (Eonset=1.0 V vs. reversible hydrogen electrode) and half-wave potential (E1/2=0.92 V). This was better than the state-of-the-art Pt/C catalyst (Eonset=1.00 V and E1/2=0.85 V) under the same conditions. Overall, the functionalized FePc/CNT-R assemblies showed enhanced ORR performance in comparison to the non-functionalized FePc/CNT assembly. The origin of this behavior was investigated using density functional theory calculations, which demonstrated that the coordination of electron-donating groups to FePc facilitated the adsorption and activation of oxygen. This study not only demonstrates a series of advanced ORR electrocatalysts, but also introduces a feasible strategy for the rational design of highly active electrocatalysts for other proton-coupled electron transfer reactions. 相似文献
88.
Sergio Calderon-Ardila Joost Matthijssen Bart Van Huffel Olivier Péruch Didier Morvan Virginie Bellière-Baca Michiel Dusselier Prof. Bert F. Sels 《ChemCatChem》2022,14(8):e202101730
Sulphides of alpha-hydroxy thioesters and esters (SAH(T)Es) are important fine chemicals and have great potential as platform molecules. SAH(T)Es are typically synthesized from fossil sources while little is known regarding their synthesis from carbohydrates. We report our findings about the one-pot chemocatalytic conversion of erythrulose (ERU) to SAH(T)Es. Sn, Mo and W chlorides were the most selective catalysts towards the synthesis of S-butyl-4-butylthio-2-hydroxybutanethioate (BBTHBT) in 1-BuSH. The selectivity towards BBTHBT was impacted by the formation of different thioacetals (TAs). The addition of either KOH, H2O or MeOH was effective to decrease TAs formation and increase selectivity towards BBTHBT (or its ester). A kinetic profile, in situ 13C NMR measurements and experiments at different temperatures complement our studies to unravel the complicated reaction network involved in the conversion of ERU to SAH(T)Es. This insight provides a solid foundation for future improvements in the sustainable synthesis of SAH(T)Es. 相似文献
89.
Lukas A. Wolzak Felix J. de Zwart Dr. Jean-Pierre H. Oudsen Dr. Stuart A. Bartlett Prof. Bas de Bruin Prof. Joost N. H. Reek Prof. Moniek Tromp Dr. Ties J. Korstanje 《ChemCatChem》2022,14(18):e202200547
Nickel-catalyzed cross-coupling reactions have become a powerful methodology to construct C-heteroatom bonds. However, many protocols suffer from competitive off-cycle reaction pathways and require non-equimolar amounts of coupling partners to suppress them. Here, we report on mechanistic examination of carboxylate O-arylation under thermal conditions, in both the presence and absence of an exogeneous bipyridine-ligand. Furthermore, spectroscopic studies of the novel ligand-free carboxylate O-arylation reaction unveiled the resting state of the nickel catalyst, the crucial role of the alkylamine base and the formation of an off-cycle NiI−NiII dimer upon reduction. This study provides insights into the competition between productive catalysis and deleterious pathways (comproportionation and protodehalogenation) in the commonly proposed self-sustained NiI/NiIII catalytic cycle. Thereby we show that for productive nickel-catalyzed carboxylate O-arylation a choice must be made between either mild conditions or equimolar ratios of substrates. 相似文献
90.
Dr. Catriona C. James Dinghao Wu Dr. Eduard O. Bobylev Prof. Alexander Kros Prof. Bas de Bruin Prof. Joost N. H. Reek 《ChemCatChem》2022,14(23):e202200942
Gold catalysts exhibit poor compatibility with cellular components. We show that encapsulation of a gold catalyst within the cavity of a supramolecular cage improves the reactivity of the gold complex under biological conditions. The gold complex catalyzes an intramolecular hydroarylation to produce a fluorescent dye. The encapsulated gold is able to produce this dye in higher yields compared to the free gold under aqueous aerobic conditions and in the presence of biological additives. The substrate was found to be highly cytotoxic, meaning that a very low substrate concentration of 1 μM is required to carry its transformation inside living cells; however, catalysis in cell culture media carried out at micromolar range is found to be inhibited. Although this specific reaction cannot be applied inside living cells, we present a viable strategy to improve the reactivity of gold catalysts in vivo. 相似文献