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1.
For a number of phosphoryltransfer enzymes, including the exonuclease subunit of DNA polymerase I, a mechanism involving two-metal ions and double Lewis-acid activation of the substrate, combined with leaving group stabilization, has been proposed. Inspired by the active site structure of this enzyme, we have designed as a synthetic phosphoryl transfer catalyst the dicopper(II) macrocyclic complex LCu(2). Crystal structures of complexes [(L)Cu(2)(mu-NO(3))(NO(3))](NO(3))(2) (1), [(L)Cu(2)(mu-CO(3))(CH(3)OH)](BF(4))(2) (2), and [(L)Cu(2)(mu-O(2)P(OCH(3))(2))(NO(3))](NO(3))(2) (3) illustrate various possibilities for the interaction of oxoanions with the dicopper(II) site. 1 efficiently promotes the transesterification of dimethyl phosphate (DMP) in CD(3)OD, k(cat) = 2 x 10(-)(4) s(-)(1) at 55 degrees C. 1 is the only available catalyst for the smooth transesterification of highly inert simple dialkyl phosphates. From photometric titrations and the pH dependence of reactivity, we conclude that a complex [(L)Cu(2)(DMP)(OCH(3))](2+) is the reactive species. Steric bulk at the -OR substituents of phosphodiester substrates O(2)P(OR)(2)(-) drastically reduces the reactivity of 1. This is explained with -OR leaving group stabilization by Cu coordination, an interaction which is sensitive to steric crowding at the alpha-C-atom of substituent R. A proposed reaction mechanism related to that of the exonuclease unit of DNA polymerase I is supported by DFT calculations on reaction intermediates. The complex [(L)Cu(3)(mu(3)-OH)(mu-CH(3)O)(2)(CH(3)CN)(2)](ClO(4))(3) (4) incorporates a [Cu(OH)(OCH(3))(2)(CH(3)CN)(2)](-) complex anion, which might be considered as an analogue of the [PO(2)(OCH(3))(2)(OCD(3))](2)(-) transition state (or intermediate) of DMP transesterification catalyzed by LCu(2).  相似文献   
2.
During metal welding and cutting, large amounts of particulate matter (PM) are produced that might represent a significant health risk for the exposed workers. In the present pilot study, we performed an elemental analysis of fine PM collected in a metal workshop. Also, elemental analysis of the hair and nail samples collected from workers exposed to the workshop dust and control group was done. Concentrations of 15 elements in PM were measured with X‐Ray Fluorescence (XRF) and Particle Induced X‐ray Emission (PIXE), whereas inductively coupled plasma mass spectrometry (ICP‐MS) was used to determine 12 elements in hair and nail samples. Mean 8‐hr concentrations of PM2.5, Fe, and Mn in the vicinity of welders were up to 1803, 860, and 30 μg/m3, respectively, whereas in the nearby city, daily PM2.5 concentrations are on average 11 μg/m3. We found that several elements, especially Fe and Mn, had substantially higher concentrations in hair and nail samples of exposed workers than in the control group, which indicates the accumulation of metals in workers' tissues, although limit values were not exceeded.  相似文献   
3.
Elastic electron deuteron scattering was measured at the Bonn 2.5 GeV Electron-Synchrotron using a two spectrometer coincidence technique. Data were taken at values of the four momentum transfer squaredQ 2=0.50, 0.60, 0.78, 1.00, and 1.3 (GeV/c)2 at electron scattering angles θ e =77.5° to 139.0° in order to separate the magnetic dipole formfactorF M (Q 2) from the electric formfactorF E (Q 2). Experimental cross sections are compared to theoretical predictions and to measurements of other laboratories. The results indicate that contributions from meson exchange currents are not negligible in thisQ 2 region.  相似文献   
4.
The self‐regenerative property of LaCo1–xyPdx Zny O3±δ and LaFe1–xyPdx Zny O3±δ solid solutions with monometallic Pd or bimetallic Pd/Zn substituents for Co or Fe is studied under a redox cycle by high angular annular dark‐field scanning transmission electron microscopy (STEM‐HAADF) and energy dispersive X‐ray spectroscopy (EDX) and X‐ray diffraction (XRD). These results reveal that the composition of perovskites determines the self‐regenerative property that occurs largely in LaCo1–xyPdx Zny O3±δ but is limited greatly in LaFe1–xyPdx Zny O3±δ. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)  相似文献   
5.
The NMR conformational study of three asymmetric phenylindenylidene ruthenium complexes 4.1–4.3, is presented. Complete 1H and 13C assignments could be obtained for 4.1–4.3 in benzene solution from multiple 2D homonuclear and heteronuclear NMR techniques. Our NMR analysis shows that each complex exists as a 55:45 mixture of two rotational isomers in slow exchange on the NMR chemical shift timescale. They are shown to be related by a 180° flip of the indenylidene ligand along the Ru?CR bond. Both rotational isomers can be discriminated by means of NOEs contacts between the various ligands coordinating to the Ru. By matching these stereospecific assignments to the chemical shift, a chemical shift based fingerprint of the isomers that may allow straightforward assignment of future asymmetric phenylindenylidene ruthenium complexes is proposed. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
6.
A concise overview is given on mononuclear and dinuclear, bidentate Schiff base ruthenium complexes with different additional ligands and on their applications in various chemical transformations such as Kharasch addition, enol-ester synthesis, alkyne dimerization, olefin metathesis and atom transfer radical polymerization. These new ruthenium complexes, conveniently prepared from commonly available ruthenium compounds, are very stable, exhibit a good tolerance towards organic functionalities, air and moisture and display high activity and chemoselectivity in chemical transformations. Relevant features of coordination chemistry connected with the reaction mechanism and chemoselectivity are also fully described. Since the nature of Schiff bases can be changed in a variety of ways, appealing routes for designing and preparing novel ruthenium complexes can be foreseen in the future.  相似文献   
7.
The objective of this work was to develop an industrially relevant olefin metathesis initiator, which circumvents the expensive, patent protected, often cumbersome preparative routes via Grubbs benzylidene complexes. Upon coordination of a Schiff base ligand to a second-generation ruthenium allenylidene complex, the formation of three catalyst isomers was observed. The major isomer was successfully isolated, and tested in a few olefin metathesis reactions. Acids such as HCl and HSiCl(3) were found to boost the metathesis reaction but the in situ formation of a neutral Ru carbyne complex restricted the catalytic capacity. Using the Lewis acid PhSiCl(3), the formation of a carbyne species was avoided, and turnover numbers up to 30,000 were reached in the ring-opening metathesis polymerisation of cycloocta-1,5-diene.  相似文献   
8.
Polyhydroxyalkanoates (PHAs) are biodegradable, biocompatible polyesters and very attractive candidates for biomedical applications as materials for tissue engineering. They have a hydrophobic character, but some are able to spread at the air-water interface to form monomolecularly thin films (Langmuir monolayers). This is a very convenient model to analyze PHA self-assembly in two dimensions and to study their molecular interactions with other amphiphilic compounds, which is very important considering compatibility between biomaterials and cell membranes. We used the Langmuir monolayer technique and Brewster angle microscopy to study the properties of poly([R]-3-hydroxy-10-undecenoate) (PHUE) films on the free water surface in various experimental conditions. Moreover, we investigated the interactions between the polymer and one of the main biomembrane components, 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). The addition of lipid to a polymer film does not change the monolayer phase behavior; however, the interactions between these two materials are repulsive and fall in two composition-dependent regimes. In summary, this is the first systematic study of the monolayer behavior of PHUE, thus forming a solid basis for a thorough understanding of material interactions, in particular in the context of biomaterials and implants.  相似文献   
9.
Glassy carbon electrode (GCE) coated with anisotropic gold nanoplates (aAuNPs) was used for the study of oxygen reduction reaction (ORR) in 0.5 M sulfuric acid instead of bulk gold electrodes. The electrode cleaning/activation procedure lead to the removal of any charged and uncharged residues on the gold nanoplates, leaving the nanostructured surface highly active towards oxygen reduction. The advantages: much lower overpotential and larger current densities of oxygen reduction are ascribed to the unique nanostructures present on the carbon electrode surface‐the gold nanoplates. They are rich in edges providing a large population of Au (100) sites with unsaturated coordination exposed to the solution, and catalytically active. Measurements performed using a rotating disc electrode, modified with the gold nanoplates, confirmed that ORR proceeds via two separate steps: oxygen is reduced to hydrogen peroxide, and the peroxide is further reduced in a two‐electron reduction to water.  相似文献   
10.
A straightforward pyrrole synthesis from diallylamines is developed by using a tandem catalyst system leading to ring-closing metathesis with the second generation Grubbs’ catalyst (10%) followed by dehydrogenation in the presence of RuCl3 × H2O (2%).  相似文献   
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