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191.
Ross F. Koby Alicia M. Doerr Nicholas R. Rightmire Nathan D. Schley Brian K. Long Timothy P. Hanusa 《Angewandte Chemie (International ed. in English)》2020,59(24):9542-9548
Milling two equivalents of K[1,3‐(SiMe3)2C3H3] (=K[A′]) with MgX2 (X=Cl, Br) produces the allyl complex [K2MgA′4] ( 1 ). Crystals grown from toluene are of the solvated species [((η6‐tol)K)2MgA′4] ([ 1 ?2(tol)]), a trimetallic monomer with both bridging and terminal (η1) allyl ligands. When recrystallized from hexanes, the unsolvated 1 forms a 2D coordination polymer, in which the Mg is surrounded by three allyl ligands. The C?C bond lengths differ by only 0.028 Å, indicating virtually complete electron delocalization. This is an unprecedented coordination mode for an allyl ligand bound to Mg. DFT calculations indicate that in isolation, an η3‐allyl configuration on Mg is energetically preferred over the η1‐ (σ‐bonded) arrangement, but the Mg must be in a low coordination environment for it to be experimentally realized. Methyl methacrylate is effectively polymerized by 1 , with activities that are comparable to K[A′] and greater than the homometallic magnesium complex [{MgA′2}2]. 相似文献
192.
Bentian Zhang Gengtao Fu Yutao Li Lecheng Liang Nicholas S. Grundish Yawen Tang John B. Goodenough Zhiming Cui 《Angewandte Chemie (International ed. in English)》2020,59(20):7857-7863
Controllable synthesis of atomically ordered intermetallic nanoparticles (NPs) is crucial to obtain superior electrocatalytic performance for fuel cell reactions, but still remains arduous. Herein, we demonstrate a novel and general hydrogel‐freeze drying strategy for the synthesis of reduced graphene oxide (rGO) supported Pt3M (M=Mn, Cr, Fe, Co, etc.) intermetallic NPs (Pt3M/rGO‐HF) with ultrasmall particle size (about 3 nm) and dramatic monodispersity. The formation of hydrogel prevents the aggregation of graphene oxide and significantly promotes their excellent dispersion, while a freeze‐drying can retain the hydrogel derived three‐dimensionally (3D) porous structure and immobilize the metal precursors with defined atomic ratio on GO support during solvent sublimation, which is not afforded by traditional oven drying. The subsequent annealing process produces rGO supported ultrasmall ordered Pt3M intermetallic NPs (≈3 nm) due to confinement effect of 3D porous structure. Such Pt3M intermetallic NPs exhibit the smallest particle size among the reported ordered Pt‐based intermetallic catalysts. A detailed study of the synthesis of ordered intermetallic Pt3Mn/rGO catalyst is provided as an example of a generally applicable method. This study provides an economical and scalable route for the controlled synthesis of Pt‐based intermetallic catalysts, which can pave a way for the commercialization of fuel cell technologies. 相似文献
193.
Nan Wu Po‐Hsiu Chien Yumin Qian Yutao Li Henghui Xu Nicholas S. Grundish Biyi Xu Haibo Jin Yan‐Yan Hu Guihua Yu John B. Goodenough 《Angewandte Chemie (International ed. in English)》2020,59(10):4131-4137
Li+‐conducting oxides are considered better ceramic fillers than Li+‐insulating oxides for improving Li+ conductivity in composite polymer electrolytes owing to their ability to conduct Li+ through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li+‐insulating oxides (fluorite Gd0.1Ce0.9O1.95 and perovskite La0.8Sr0.2Ga0.8Mg0.2O2.55) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)‐based polymer composite electrolytes, each with a Li+ conductivity above 10?4 S cm?1 at 30 °C. Li solid‐state NMR results show an increase in Li+ ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2‐site occupancy originates from the strong interaction between the O2? of Li‐salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li+ transport. All‐solid‐state Li‐metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 °C. 相似文献
194.
Nicholas C. Nelson Linxiao Chen Debora Meira Libor Kovarik Jnos Szanyi 《Angewandte Chemie (International ed. in English)》2020,59(40):17657-17663
The application of single‐atom catalysts (SACs) to high‐temperature hydrogenation requires materials that thermodynamically favor metal atom isolation over cluster formation. We demonstrate that Pd can be predominantly dispersed as isolated atoms onto TiO2 during the reverse water–gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO2 surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO2) with neat TiO2 prior to the rWGS reaction. The in situ dispersion of Pd was reflected through a continuous increase of rWGS activity over 92 h and supported by kinetic analysis, infrared and X‐ray absorption spectroscopies and scanning transmission electron microscopy. The thermodynamic stability of Pd under high‐temperature rWGS conditions is associated with Pd‐Ti coordination, which manifests upon O‐vacancy formation, and the artificial increase in TiO2 surface area. 相似文献
195.
196.
DNA-templated Ag nanocluster formation 总被引:2,自引:0,他引:2
The high affinity of Ag+ for DNA bases has enabled creation of short oligonucleotide-encapsulated Ag nanoclusters without formation of large nanoparticles. Time-dependent formation of cluster sizes ranging from Ag1 to Ag4/oligonucleotide were observed with strong, characteristic electronic transitions between 400 and 600 nm. The slow nanocluster formation kinetics enables observation of specific aqueous nanocluster absorptions that evolve over a period of 12 h. Induced circular dichroism bands confirm that the nanoclusters are associated with the chiral ss-DNA template. Fluorescence, absorption, mass, and NMR spectra all indicate that multiple species are present, but that their creation is both nucleotide- and time-dependent. 相似文献
197.
The attachment of particles to bubbles in solution is of fundamental importance to several industrial processes, most notably in the process of froth flotation. During this process hydrophobic particles attach to air bubbles in solution, which allows them to be separated as froth at the surface. The addition of chemicals can help to modulate these interactions to increase the yield of the minerals of interest. Over the past decade the atomic force microscope (AFM) has been adapted for use in studying the forces involved in the attachment of single particles to bubbles in the laboratory. This allows the measurement of actual DLVO (Derjaguin, Landau, Vervey and Overbeek) forces and adhesive contacts to be measured under different conditions. In addition contact angles may be calculated from features of force versus distance curves. It is the purpose of this article to illustrate how the colloid probe technique can be used to make single particle-bubble interactions and to summarise the current literature describing such experiments. 相似文献
198.
Large Zero‐Field Splittings of the Ground Spin State Arising from Antisymmetric Exchange Effects in Heterometallic Triangles 下载免费PDF全文
Samantha A. Magee Dr. Stephen Sproules Dr. Anne‐Laure Barra Dr. Grigore A. Timco Nicholas F. Chilton Prof. David Collison Prof. Richard E. P. Winpenny Prof. Eric J. L. McInnes 《Angewandte Chemie (International ed. in English)》2014,53(21):5310-5313
[Ru2Mn(O)(O2CtBu)6(py)3] has an S=5/2 ground state with a very large zero‐field splitting (ZFS) of D=2.9 cm?1, as characterized by EPR spectroscopy at 4–330 GHz. This is far too large to be due to the MnII ion (D <0.2 cm?1), as shown from the {Fe2Mn} analogue, but can be modeled by antisymmetric exchange effects. 相似文献
199.
200.
Thane H. Taylor Nicholas W. Frost Michael T. Bowser Edgar A. Arriaga 《Analytical and bioanalytical chemistry》2014,406(6):1683-1691
Mitochondria are responsible for maintaining a variety of cellular functions. One such function is the interaction and subsequent import of proteins into these organelles via the translocase of outer membrane (TOM) complex. Antibodies have been used to analyze the presence and function of proteins comprising this complex, but have not been used to investigate variations in the abundance of TOM complex in mitochondria. Here, we report on the feasibility of using capillary cytometry with laser-induced fluorescence to detect mitochondria labeled with antibodies targeting the TOM complex and to estimate the number of antibodies that bind to these organelles. Mitochondria were fluorescently labeled with DsRed2, while antibodies targeting the TOM22 protein, one of nine proteins comprising the TOM complex, were conjugated to the Atto-488 fluorophore. At typical labeling conditions, 94 % of DsRed2 mitochondria were also immunofluorescently labeled with Atto-488 Anti-TOM22 antibodies. The calculated median number of Atto-488 Anti-TOM22 antibodies bound to the surface of mitochondria was ~2,000 per mitochondrion. The combination of fluorescent immunolabeling and capillary cytometry could be further developed to include multicolor labeling experiments, which enable monitoring several molecular targets at the same time in the same or different organelle types. Figure
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