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101.
Alfred D. French Monica Concha Michael K. Dowd Edwin D. Stevens 《Cellulose (London, England)》2014,21(2):1051-1063
Introductory material first describes electron density approaches and demonstrates visualization of electron lone pairs and bonding as concentrations of electron density. Then it focuses on the application of Bader’s Quantum Theory of Atoms-in-Molecules (AIM) to cellulose models. The purpose of the work is to identify the various interactions that stabilize cellulose structure. AIM analysis aids study of non-covalent interactions, especially those for which geometric criteria are not well established. The models were in the form of pairs of cellotriose molecules, methylated at the O1 and O4 ends. Based on the unit cell of cellulose Iβ, there were corner–corner, and center–center pairs that correspond to (200) sheets, and corner–center pairings that corresponded to (1–10) and (110) stacks. AIM analysis (or charge-density topology analysis) was applied before and after minimization in vacuum and in continuum solvation. Besides the conventional O–H···O hydrogen bonds, all of which were known from geometric criteria, C–H···O hydrogen bonds (some previously reported), and some O···O and H···H interactions were found. Non-covalent bonds in the (200) sheets were maintained in all calculations with the exception of a weak, bifurcated O6–H···O2′′ bond that was not found in the corner–corner pair model and did not survive minimization. Nor did the O6···O4 interactions on the reducing ends of the triosides. Pairs of molecules along the (110) plane had an equal number (12) of non-covalent bonds compared to the pairs along the (1–10) plane, but the AIM parameters indicated the bonds between the pairs in the (110) plane were weaker. Intra-molecular O–H···O hydrogen bonds survived in these minimized pairs, but the relative chain alignments usually did not. 相似文献
102.
Highly Stable Water‐Soluble Platinum Nanoparticles Stabilized by Hydrophilic N‐Heterocyclic Carbenes 下载免费PDF全文
Edwin A. Baquero Dr. Simon Tricard Dr. Juan Carlos Flores Prof. Dr. Ernesto de Jesús Prof. Dr. Bruno Chaudret 《Angewandte Chemie (International ed. in English)》2014,53(48):13220-13224
Controlling the synthesis of stable metal nanoparticles in water is a current challenge in nanochemistry. The strategy presented herein uses sulfonated N‐heterocyclic carbene (NHC) ligands to stabilize platinum nanoparticles (PtNPs) in water, under air, for an indefinite time period. The particles were prepared by thermal decomposition of a preformed molecular Pt complex containing the NHC ligand and were then purified by dialysis and characterized by TEM, high‐resolution TEM, and spectroscopic techniques. Solid‐state NMR studies showed coordination of the carbene ligands to the nanoparticle surface and allowed the determination of a 13C–195Pt coupling constant for the first time in a nanosystem (940 Hz). Additionally, in one case a novel structure was formed in which platinum(II) NHC complexes form a second coordination sphere around the nanoparticle. 相似文献
103.
Howard Yi Fan Sim Jaslyn Ru Ting Chen Charlynn Sher Lin Koh Dr. Hiang Kwee Lee Dr. Xuemei Han Gia Chuong Phan-Quang Jing Yi Pang Dr. Chee Leng Lay Dr. Srikanth Pedireddy Dr. In Yee Phang Prof. Edwin Kok Lee Yeow Prof. Xing Yi Ling 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17145-17151
The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mgcat−1 h−1 under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst–N2 interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-NZIF interaction is key to enable strong N2 adsorption over H atom. 相似文献
104.
Valentin Chabert Lucille Babel Michael P. Füeg Maksym Karamash Edwin S. Madivoli Nelly Herault Joana M. Dantas Carlos A. Salgueiro Bernd Giese Katharina M. Fromm 《Angewandte Chemie (International ed. in English)》2020,59(30):12331-12336
Anaerobic microorganisms of the Geobacter genus are effective electron sources for the synthesis of nanoparticles, for bioremediation of polluted water, and for the production of electricity in fuel cells. In multistep reactions, electrons are transferred via iron/heme cofactors of c‐type cytochromes from the inner cell membrane to extracellular metal ions, which are bound to outer membrane cytochromes. We measured electron production and electron flux rates to 5×105 e s?1 per G. sulfurreducens. Remarkably, these rates are independent of the oxidants, and follow zero order kinetics. It turned out that the microorganisms regulate electron flux rates by increasing their Fe2+/Fe3+ ratios in the multiheme cytochromes whenever the activity of the extracellular metal oxidants is diminished. By this mechanism the respiration remains constant even when oxidizing conditions are changing. This homeostasis is a vital condition for living systems, and makes G. sulfurreducens a versatile electron source. 相似文献
105.
Measurement of emerging dechloranes in human serum using modulated gas chromatography coupled to electron capture negative ionization time‐of‐flight mass spectrometry 下载免费PDF全文
106.
Sukhorukov GB Susha AS Davis S Leporatti S Donath E Hartmann J Möhwald H 《Journal of colloid and interface science》2002,247(1):251-254
Hollow polymer shells formed by layer-by-layer adsorption of oppositely charged polyelectrolytes onto micrometer-sized colloidal particles with subsequent decomposition of the colloidal core were employed as a model system for the study of inorganic crystallization reactions in restricted volumes. The size-selective permeability of shells is used for spatially controlling the precipitation of inorganic salts CaCO3 and BaCO3 into the shell interior. Outside the shells the precipitation was suppressed by the polymers, which are unable to penetrate the shell wall. The precipitates were studied by scanning electron microscopy and atomic force microscopy. The fundamental and applied aspects of research on spatially confined synthesis of inorganic particles are under discussion. 相似文献
107.
A synthetic procedure for the preparation of the unusual charge-separated pyridinium barbiturate zwitterion 2 from 1,3-dimethylbarbituric acid and 2-pyridinecarbaldehyde in methanol was developed. The structure of the compound was confirmed with X-ray analysis to demonstrate the strong charge separation throughout the molecule. One would expect that this charge separation would increase its reactivity; however, contrary to this expectation, the compound is very stable in acidic media, and in the presence of a base, decarbonylation occurs on one barbituric acid while the zwitterionic moiety of the molecule stays intact. 相似文献
108.
Villa de P AL Alarcón E Montes de Correa C 《Chemical communications (Cambridge, England)》2002,(22):2654-2655
MCM-41 was found to be an active heterogeneous catalyst for the synthesis of nopol by the Prins condensation of beta-pinene and paraformaldehyde, but Sn-MCM-41 in which Sn has been grafted on MCM-41 by chemical vapor deposition is far more active and combines high efficiency and recyclability. 相似文献
109.
110.
Alexander Kreuzer 《Geometriae Dedicata》1999,76(1):43-52
This note deals with the following question: How many planes of a linear space (P, $\mathfrak{L}$ ) must be known as projective planes to ensure that (P, $\mathfrak{L}$ ) is a projective space? The following answer is given: If for any subset M of a linear space (P, $\mathfrak{L}$ ) the restriction (M, $\mathfrak{L}$ )(M)) is locally complete, and if for every plane E of (M, $\mathfrak{L}$ (M)) the plane $\bar E$ generated by E is a projective plane, then (P, $\mathfrak{L}$ ) is a projective space (cf. 5.6). Or more generally: If for any subset M of P the restriction (M, $\mathfrak{L}$ (M)) is locally complete, and if for any two distinct coplanar lines G1, G2 ∈ $\mathfrak{L}$ (M) the lines $\bar G_1 ,\bar G_2 \varepsilon \mathfrak{L}$ generated by G1, G2 have a nonempty intersection and $\overline {G_1 \cup {\text{ }}G_2 }$ satisfies the exchange condition, then (P, $\mathfrak{L}$ ) is a generalized projective space. 相似文献