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91.
Dr. Yann Gloaguen Christophe Rebreyend Dr. Martin Lutz Pravin Kumar Dr. Martina Huber Dr. Ir. Jarl Ivar van der Vlugt Prof. Dr. Sven Schneider Prof. Dr. Bas de Bruin 《Angewandte Chemie (International ed. in English)》2014,53(26):6814-6818
Photochemical activation of [(PNNH)Rh(N3)] (PNNH=6‐di‐(tert‐butyl)phosphinomethyl‐2,2′‐bipyridine) complex 2 produced the paramagnetic (S=1/2), [(PNN)Rh?N.‐Rh(PNN)] complex 3 (PNN?=methylene‐deprotonated PNNH), which could be crystallographically characterized. Spectroscopic investigation of 3 indicates a predominant nitridyl radical (.N2?) character, which was confirmed computationally. Complex 3 reacts selectively with CO, producing two equivalents of [(PNN)RhI(CO)] complex 4 , presumably by nitridyl radical N,N‐coupling. 相似文献
92.
Adsorption of Large Hydrocarbons on Coinage Metals: A van der Waals Density Functional Study
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The adsorption of organic molecules onto the close‐packed facets of coinage metals is studied, and how accurately adsorption heights can be described by using recent advances of the van der Waals density functional (vdWDF), with optPBE/vdWDF, optB86b/vdWDF, vdWDF2, and rev/vdWDF2 functionals is illustrated. The adsorption of two prototypical aromatic hydrocarbons is investigated, and the calculated adsorption heights are compared to experimental literature values from normal incident X‐ray standing wave absorption and a state‐of‐the‐art semi‐empirical method. It is shown that both the optB86b/vdWDF and rev/vdWDF2 functionals describe adsorption heights with an accuracy of 0.1 Å, compared to experimental values, and are concluded as reliable methods of choice for related systems. 相似文献
93.
Anja Müller Katia Sparnacci Wolfgang E.S. Unger Sven Tougaard 《Surface and interface analysis : SIA》2020,52(11):770-777
Most real core-shell nanoparticle (CSNP) samples deviate from an ideal core-shell structure potentially having significant impact on the particle properties. An ideal structure displays a spherical core fully encapsulated by a shell of homogeneous thickness, and all particles in the sample exhibit the same shell thickness. Therefore, analytical techniques are required that can identify and characterize such deviations. This study demonstrates that by analysis of the inelastic background in X-ray photoelectron spectroscopy (XPS) survey spectra, the following types of deviations can be identified and quantified: the nonuniformity of the shell thickness within a nanoparticle sample and the incomplete encapsulation of the cores by the shell material. Furthermore, CSNP shell thicknesses and relative coverages can be obtained. These results allow for a quick and straightforward comparison between several batches of a specific CSNP, different coating approaches, and so forth. The presented XPS methodology requires a submonolayer distribution of CSNPs on a substrate. Poly(tetrafluoroethylene)-poly(methyl methacrylate) and poly(tetrafluoroethylene)-polystyrene polymer CSNPs serve as model systems to demonstrate the applicability of the approach. 相似文献
94.
Philip Boehm Sven Roediger Alessandro Bismuto Bill Morandi 《Angewandte Chemie (International ed. in English)》2020,59(41):17887-17896
An efficient palladium‐catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high‐value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl‐containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO. 相似文献
95.
Liesbeth Tytgat Matthias R. Kollert Lana Van Damme Hugo Thienpont Heidi Ottevaere Georg N. Duda Sven Geissler Peter Dubruel Sandra Van Vlierberghe Taimoor H. Qazi 《Macromolecular bioscience》2020,20(4)
Adipose tissue engineering aims to provide solutions to patients who require tissue reconstruction following mastectomies or other soft tissue trauma. Mesenchymal stromal cells (MSCs) robustly differentiate into the adipogenic lineage and are attractive candidates for adipose tissue engineering. This work investigates whether pore size modulates adipogenic differentiation of MSCs toward identifying optimal scaffold pore size and whether pore size modulates spatial infiltration of adipogenically differentiated cells. To assess this, extrusion‐based 3D printing is used to fabricate photo‐crosslinkable gelatin‐based scaffolds with pore sizes in the range of 200–600 µm. The adipogenic differentiation of MSCs seeded onto these scaffolds is evaluated and robust lipid droplet formation is observed across all scaffold groups as early as after day 6 of culture. Expression of adipogenic genes on scaffolds increases significantly over time, compared to TCP controls. Furthermore, it is found that the spatial distribution of cells is dependent on the scaffold pore size, with larger pores leading to a more uniform spatial distribution of adipogenically differentiated cells. Overall, these data provide first insights into the role of scaffold pore size on MSC‐based adipogenic differentiation and contribute toward the rational design of biomaterials for adipose tissue engineering in 3D volumetric spaces. 相似文献
96.
Emo Chiellini Giancarlo Galli Sven T. Lagerwall Lachezar Komitov 《Macromolecular Symposia》1995,96(1):79-94
The scope for the synthesis and investigation of chiral smectic A liquid crystalline (LC) polymers and block copolymers is discussed. LC block copolymers can combine the molecular order of liquid crystals and the supramolecular order typical of block copolymers, thus allowing to attain information on mesomorphic responses in restricted geometries. We present a general overview on several aspects of the syntheses and properties of LC block copolymers, specifically those obtained by starting from azomacroinitiators. These materials can exhibit an electroclinic effect, that is an electrically induced molecular tilt, which is characterized by a linear dependence on the applied field and a very fast response time in the paraelectric smectic A phase. The current progress in their potential application in electrooptics is outlined. 相似文献
97.
Activation of a Photodissociative Ruthenium Complex by Triplet–Triplet Annihilation Upconversion in Liposomes
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Sven H. C. Askes Azadeh Bahreman Dr. Sylvestre Bonnet 《Angewandte Chemie (International ed. in English)》2014,53(4):1029-1033
Liposomes capable of generating photons of blue light in situ by triplet–triplet annihilation upconversion of either green or red light, were prepared. The red‐to‐blue upconverting liposomes were capable of triggering the photodissociation of ruthenium polypyridyl complexes from PEGylated liposomes using a clinical grade photodynamic therapy laser source (630 nm). 相似文献
98.
Michael G. Pfeffer Tanja Kowacs Dr. Maria Wächtler Dr. Julien Guthmuller Prof. Dr. Benjamin Dietzek Prof. Dr. Johannes G. Vos Prof. Dr. Sven Rau 《Angewandte Chemie (International ed. in English)》2015,54(22):6627-6631
A molecular photocatalyst consisting of a RuII photocenter, a tetrapyridophenazine bridging ligand, and a PtX2 (X=Cl or I) moiety as the catalytic center functions as a stable system for light‐driven hydrogen production. The catalytic activity of this photochemical molecular device (PMD) is significantly enhanced by exchanging the terminal chlorides at the Pt center for iodide ligands. Ultrafast transient absorption spectroscopy shows that the intramolecular photophysics are not affected by this change. Additionally, the general catalytic behavior, that is, instant hydrogen formation, a constant turnover frequency, and stability are maintained. Unlike as observed for the Pd analogue, the presence of excess halide does not affect the hydrogen generation capacity of the PMD. The highly improved catalytic efficiency is explained by an increased electron density at the Pt catalytic center, this is confirmed by DFT studies. 相似文献
99.
本文使用傅里叶变换微波谱仪研究了乙基苯胺类物质(邻乙基苯胺,间乙基苯胺,对乙基苯胺)的分子结构. 由于此类分子含氮原子(I14N=1),因此跃迁谱线中都呈现出核四级裂分. 通过比较实验测定得到的分子结构,可总结苯胺环上不同位置乙基的取代对氨基及分子整体结构的影响. 相似文献