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991.
Frontispiece: NMR Fingerprints of the Drug‐like Natural‐Product Space Identify Iotrochotazine A: A Chemical Probe to Study Parkinson’s Disease 下载免费PDF全文
992.
Dr. Qing‐Fu Sun Dr. Sota Sato Prof. Dr. Makoto Fujita 《Angewandte Chemie (International ed. in English)》2014,53(49):13510-13513
In the self‐assembly of PdII ions and two different, but similarly shaped, ligands ( 1 and 2 ), neither random mixing nor self‐sorting of the two ligands into two unmixed structures was observed. Instead a mixed, yet sorted, Pd12( 1 )12( 2 )12 cantellated tetrahedron (and its pseudoisomer) was selectively formed, thus revealing a fine example of intramolecular self‐sorting. A case study showed that a homothetic ratio of >2 is necessary to observe cantellated tetrahedra. 相似文献
993.
Andrea Kunfermann Matthias Witschel Boris Illarionov Ren Martin Matthias Rottmann H. Wolfgang Hffken Michael Seet Wolfgang Eisenreich Hans‐Joachim Knlker Markus Fischer Adelbert Bacher Michael Groll Franois Diederich 《Angewandte Chemie (International ed. in English)》2014,53(8):2235-2239
The enzymes of the non‐mevalonate pathway for isoprenoid biosynthesis have been identified as attractive targets with novel modes of action for the development of herbicides for crop protection and agents against infectious diseases. This pathway is present in many pathogenic organisms and plants, but absent in mammals. By using high‐throughput screening, we identified highly halogenated marine natural products, the pseudilins, to be inhibitors of the third enzyme, IspD, in the pathway. Their activity against the IspD enzymes from Arabidopsis thaliana and Plasmodium vivax was determined in photometric and NMR‐based assays. Cocrystal structures revealed that pseudilins bind to an allosteric pocket by using both divalent metal ion coordination and halogen bonding. The allosteric mode of action for preventing cosubstrate (CTP) binding at the active site was elucidated. Pseudilins show herbicidal activity in plant assays and antiplasmodial activity in cell‐based assays. 相似文献
994.
Tetracyanoquinodimethane Reduction by Complexed Guanidinyl‐Functionalized Aromatic Compounds 下载免费PDF全文
Hendrik Herrmann Alexandra Ziesak Ute Wild Simone Leingang David Schrempp Norbert Wagner Prof. Dr. Johannes Beck Dr. Elisabeth Kaifer Prof. Dr. Hubert Wadepohl Prof. Dr. Hans‐Jörg Himmel 《Chemphyschem》2014,15(2):351-365
In this work, we report on the reduction of tetracyanoquinodimethane (TCNQ) with dicationic complexes of guanidinyl‐functionalized aromatic (GFA) electron donors. In contrast to reduction with free GFAs, milder reduction conditions were achieved, and this led to semiconducting materials with extended TCNQ π stacking. The charge on the TCNQ units was estimated from the structural data obtained by single‐crystal X‐ray diffraction analysis and from IR spectroscopic data. The electrical conductivity was studied and the activation energy of the semiconducting materials was estimated from the temperature dependence of the conductivity. 相似文献
995.
Double‐Wall Carbon Nanotube–Porphyrin Supramolecular Hybrid: Synthesis and Photophysical Studies 下载免费PDF全文
Dr. María Vizuete Dr. María J. Gómez‐Escalonilla Prof. José Luis G. Fierro Dr. Pedro Atienzar Prof. Hermenegildo García Prof. Fernando Langa 《Chemphyschem》2014,15(1):100-108
Double‐wall carbon nanotubes (DWCNTs) with pyridyl units covalently attached to the external wall through isoxazolino linkers and carboxylic groups that have been esterified by pentyl chains are synthesized. The properties of these modified DWCNTs are then compared with an analogous sample based on single‐wall carbon nanotubes (SWCNTs). Raman spectroscopy shows the presence of characteristic radial breathing mode vibrations, confirming that the samples partly retain the integrity of the nanotubes in the case of DWCNTs, including the internal and external nanotubes. Quantification of the pyridyl content for both samples (DWCNT and SWCNT derivatives) is based on X‐ray photoelectron spectroscopy and thermogravimetric profiles, showing very similar substituent load. Both pyridyl‐containing nanotubes (DWCNTs and SWCNTs) form a complex with zinc porphyrin (ZnP), as evidenced by the presence of two isosbestic points in the absorption spectra of the porphyrin upon addition of the pyridyl‐functionalized nanotubes. Supramolecular complexes based on pyridyl‐substituted DWCNTs and SWCNTs quench the emission and the triplet excited state identically, through an energy‐transfer mechanism based on pre‐assembly of the ground state. Thus, the presence of the intact inner wall in DWCNTs does not influence the quenching behavior, with respect to SWCNTs, for energy‐transfer quenching with excited ZnP. These results sharply contrast with previous ones referring to electron‐transfer quenching, in which the double‐wall morphology of the nanotubes has been shown to considerably reduce the lifetime of charge separation, owing to faster electron mobility in DWCNTs compared to SWCNTs. 相似文献
996.
Spatially Resolved Confocal Resonant Raman Microscopic Analysis of Anode‐Grown Geobacter sulfurreducens Biofilms 下载免费PDF全文
When grown on the surface of an anode electrode, Geobacter sulfurreducens forms a multi‐cell thick biofilm in which all cells appear to couple the oxidation of acetate with electron transport to the anode, which serves as the terminal metabolic electron acceptor. Just how electrons are transported through such a biofilm from cells to the underlying anode surface over distances that can exceed 20 microns remains unresolved. Current evidence suggests it may occur by electron hopping through a proposed network of redox cofactors composed of immobile outer membrane and/or extracellular multi‐heme c‐type cytochromes. In the present work, we perform a spatially resolved confocal resonant Raman (CRR) microscopic analysis to investigate anode‐grown Geobacter biofilms. The results confirm the presence of an intra‐biofilm redox gradient whereby the probability that a heme is in the reduced state increases with increasing distance from the anode surface. Such a gradient is required to drive electron transport toward the anode surface by electron hopping via cytochromes. The results also indicate that at open circuit, when electrons are expected to accumulate in redox cofactors involved in electron transport due to the inability of the anode to accept electrons, nearly all c‐type cytochrome hemes detected in the biofilm are oxidized. The same outcome occurs when a comparable potential to that measured at open circuit (?0.30 V vs. SHE) is applied to the anode, whereas nearly all hemes are reduced when an exceedingly negative potential (?0.50 V vs. SHE) is applied to the anode. These results suggest that nearly all c‐type cytochrome hemes detected in the biofilm can be electrochemically accessed by the electrode, but most have oxidation potentials too negative to transport electrons originating from acetate metabolism. The results also reveal a lateral heterogeneity (x–y dimensions) in the type of c‐type cytochromes within the biofilm that may affect electron transport to the electrode. 相似文献
997.
Electronic and Structural Properties of Highly Aluminum Ion Doped TiO2 Nanoparticles: A Combined Experimental and Theoretical Study 下载免费PDF全文
Desireé M. de los Santos Teresa Aguilar Dr. Antonio Sánchez‐Coronilla Dr. Javier Navas Dr. Norge Cruz Hernández Dr. Rodrigo Alcántara Dr. Concha Fernández‐Lorenzo Prof.Dr. Joaquín Martín‐Calleja 《Chemphyschem》2014,15(11):2267-2280
This study presents the experimental and theoretical study of highly internally Al‐doped TiO2 nanoparticles. Two synthesis methods were used and detailed characterization was performed. There were differences in the doping and the crystallinity, but the nanoparticles synthesized with the different methods share common features. Anatase to rutile transformation occurred at higher temperatures with Al doping. X‐ray photoelectron spectroscopy showed the generation of oxygen vacancies, which is an interesting feature in photocatalysis. In turn, the band‐gap energy and the valence band did not change appreciably. Periodic density functional calculations were performed to model the experimentally doped structures, the formation of the oxygen vacancies, and the band gap. Calculation of the density of states confirmed the experimental band‐gap energies. The theoretical results confirmed the presence of Ti4+ and Al3+. The charge density study and electron localization function analysis indicated that the inclusion of Al in the anatase structure resulted in a strengthening of the Ti?O bonds around the vacancy. 相似文献
998.
We report on the fabrication of a surface‐enhanced Raman scattering (SERS) platform, comprised of a three‐dimensional (3D) porous eggshell membrane (ESM) scaffold decorated with Ag nanoparticles (NPs). Both native and treated ESM were used, where the treated ESM pore size and fiber crossing density was controlled by timed exposure to hydrogen peroxide (H2O2). Ag NPs were synthesized in situ by reduction of silver nitrate with ascorbic acid. Our results demonstrate that H2O2‐treated Ag‐ESM provides a more densely packed 3D network of active material, which leads to consistently higher SERS enhancement than untreated Ag‐ESM substrates. 相似文献
999.
Kinetic Modeling of α‐Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon‐Centered Radicals 下载免费PDF全文
Paschalis D. Paraskevas Dr. Maarten K. Sabbe Prof. Marie‐Françoise Reyniers Prof. Dr. Nikos Papayannakos Prof. Dr. Guy B. Marin 《Chemphyschem》2014,15(9):1849-1866
Hydrogen abstractions are important elementary reactions in a variety of reacting media at high temperatures in which oxygenates and hydrocarbon radicals are present. Accurate kinetic data are obtained from CBS‐QB3 ab initio (AI) calculations by using conventional transition‐state theory within the high‐pressure limit, including corrections for hindered rotation and tunneling. From the obtained results, a group‐additive (GA) model is developed that allows the Arrhenius parameters and rate coefficients for abstraction of the α‐hydrogen from a wide range of oxygenate compounds to be predicted at temperatures ranging from 300 to 1500 K. From a training set of 60 hydrogen abstractions from oxygenates by carbon‐centered radicals, 15 GA values (ΔGAVos) are obtained for both the forward and reverse reactions. Among them, four ΔGAVos refer to primary contributions, and the remaining 11 ΔGAVos refer to secondary ones. The accuracy of the model is further improved by introducing seven corrections for cross‐resonance stabilization of the transition state from an additional set of 43 reactions. The determined ΔGAVos are validated upon a test set of AI data for 17 reactions. The mean absolute deviation of the pre‐exponential factors (log A) and activation energies (Ea) for the forward reaction at 300 K are 0.238 log(m3 mol?1 s?1) and 1.5 kJ mol?1, respectively, whereas the mean factor of deviation <ρ> between the GA‐predicted and the AI‐calculated rate coefficients is 1.6. In comparison with a compilation of 33 experimental rate coefficients, the <ρ> between the GA‐predicted values and these experimental values is only 2.2. Hence, the constructed GA model can be reliably used in the prediction of the kinetics of α‐hydrogen‐abstraction reactions between a broad range of oxygenates and oxygenate radicals. 相似文献
1000.
Chong Zhao Dan Lei Prof. Li‐Hua Gan Dr. Zhu‐Xia Zhang Prof. Chun‐Ru Wang 《Chemphyschem》2014,15(13):2780-2784
Sc2S@C84 has recently been detected but not structurally characterized. 1 Density functional theory calculations on C84 and Sc2S@C84 show that the favored isomer of Sc2S@C84 shares the same parent cage as Sc2C2@C84, whereas Sc2S@C84:51383, which violates the isolated‐pentagon rule, is the second lowest energy isomer with the widest HOMO–LUMO gap and shows high kinetic stability. The analysis shows that Sc2S@C84:51575 is favored when the temperature exceeds 2 800 K and it can transform into the most favorable isomer Sc2S@C84:51591. Molecular orbital analysis indicates that both Sc2S and Sc2C2 formally transfer four electrons to the cage, and quantum theory of atoms in molecules analysis demonstrates that there is a covalent interaction between Sc2S and C84:51591. The IR spectra of Sc2S@C84 are provided to aid future structural identification. 相似文献