排序方式: 共有39条查询结果,搜索用时 15 毫秒
31.
We investigate via density functional theory (DFT) the appearance of small MgO-supported gold clusters with 8 to 20 atoms in a scanning tunneling microscope (STM) experiment. Comparison of simulations of ultrathin films on a metal support with a bulk MgO leads to similar results for the cluster properties relevant for STM. Simulated STM pictures show the delocalized states of the cluster rather than the atomic structure. This finding is due to the presence of s- derived delocalized states of the cluster near the Fermi energy. The properties of theses states can be understood from a jellium model for monovalent gold. 相似文献
32.
We have employed Density Functional Theory calculations to study the adsorption of CN, CN? and KCN on Au(111) and Au(211) surfaces and compare the obtained results to CO. The adsorption of CN, CN?, and KCN are exothermic with respect to the gas-phase moieties, and the adsorption energy increases at steps. Our results show that the binding mechanism of CN? is different from that of CO. The projected LDOS indicates that the bond between the flat surface and CN shows very small overlap between metal and CN states. This overlap increases provided that extra charge is present or low-coordinated Au atoms are available. Charge transfer is analyzed via the Bader method and the Electron Localization Function. Both suggest that Au–CN bonding resembles that in the gas-phase [Au(CN)2]?, which has been identified as covalent. The present study justifies the mechanism described in the literature involving a first CN? adsorption, electron transfer to form AuCN, and second adsorption of a CN? to form the soluble species and dissolve gold atoms from low grade ores. 相似文献
33.
Yrjö Hiltunen Jukka Jokisaari Anja Pulkkinen Taito Väänänen 《Chemical physics letters》1984,109(5):509-513
The structure of benzene dissolved in various thermotropic nematic liquid crystals has been studied. 13C-methane was used as an internal “deformation reference”. The results indicate that the HH distance ratios obtained front the direct dipole-dipole coupling constants correspond to the hexagon values in cases where benzene is dissolved in mixtures of nematic liquid crystals which produce negligible dipolar CH splittings for methane. The ratio rCH/r CC for benzene is in good accord with the value obtained by other spectroscopic means. The proton structure of benzene in the smectic and nematic phases of p,p′-di-n-heptylazoxybenzene (HAB), however, does not follow the general trend observed in the purely nematic phases. But the dipolar CH splitting of methane also behaves inconsistently. 相似文献
34.
Mikko Karesoja Harri Jokinen Erno Karjalainen Petri Pulkkinen Mika Torkkeli Antti Soininen Janne Ruokolainen Heikki Tenhu 《Journal of polymer science. Part A, Polymer chemistry》2009,47(12):3086-3097
11‐(2‐Bromo‐2‐methyl)propionyl‐oxy‐undecyl trichlorosilane atom transfer radical polymerization (ATRP) initiator was covalently attached on montmorillonite clay platelets via silylation reactions. The initiator clay was used to polymerize butyl acrylate (BuA) and methyl methacrylate (MMA) on the clay surface. Polymerization was performed in bulk monomer solution or in DMSO. Polymer modified clay was mixed with a poly(BuA‐co‐MMA) matrix. Small angle X‐ray scattering (SAXS) and transmission electron microscopy (TEM) showed that clay modified in DMSO gave exfoliated composites when mixed with the matrix copolymer. Mechanical properties of the composites were studied by dynamic mechanical thermal analysis (DMTA). The results showed that the mechanical properties were improved as a function of clay content, as well with an increasing homogeneity of the nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3086–3097, 2009 相似文献
35.
Otto Pulkkinen 《Journal of statistical physics》2007,128(6):1289-1305
The stationary states of boundary driven zero-range processes in random media with quenched disorder are examined, and the
motion of a tagged particle is analyzed. For symmetric transition rates, also known as the random barrier model, the stationary
state is found to be trivial in absence of boundary drive. Out of equilibrium, two further cases are distinguished according
to the tail of the disorder distribution. For strong disorder, the fugacity profiles are found to be governed by the paths
of normalized α-stable subordinators. The expectations of integrated functions of the tagged particle position are calculated for three types
of routes. 相似文献
36.
Dr. Alessandro Longo Dr. Ewoud J. J. de Boed Dr. Nisha Mammen Dr. Marte van der Linden Prof. Dr. Karoliina Honkala Prof. Dr. Hannu Häkkinen Prof. Dr. Petra E. de Jongh Dr. Baira Donoeva 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(31):7051-7058
Controlling the size and uniformity of metal clusters with atomic precision is essential for fine-tuning their catalytic properties, however for clusters deposited on supports, such control is challenging. Here, by combining X-ray absorption spectroscopy and density functional theory calculations, it is shown that supports play a crucial role in the evolution of monolayer-protected clusters into catalysts. Based on the acidic nature of the support, cluster-support interactions lead either to fragmentation of the cluster into isolated Au–ligand species or ligand-free metallic Au0 clusters. On Lewis acidic supports that bind metals strongly, the latter transformation occurs while preserving the original size of the metal cluster, as demonstrated for various Aun sizes. These findings underline the role of the support in the design of supported catalysts and represent an important step toward the synthesis of atomically precise supported nanomaterials with tailored physico-chemical properties. 相似文献
37.
Catalytic groundwater remediation from chlorinated organic solvents like trichloroethene (TCE) has been found to be more effective and sustainable than traditional non-destructive methods. Among the experimentally studied catalyst materials, Pd-decorated Au nanoparticles show the highest activity and selectivity combined with the best resistance towards poisoning by chemicals present in groundwater. In this study the thermochemistry and adsorption geometries of TCE and its hydrodechlorination products are investigated via density functional theory calculations. Various model systems for Pd-supported Au nanoparticles are addressed. The adsorption of TCE is endothermic on bare Au(111), almost thermoneutral or slightly exothermic on Pd-Au surface alloys and clearly exothermic on Pd overlayer structures on Au(111). The strongest chemisorption is on the di-σ configuration between Pd atoms over the smallest 2D Pd clusters containing only a few Pd atoms. These are not, however, the best catalysts as they are too small to co-adsorb hydrogen needed for hydrodechlorination reaction. We demonstrate good correlation between adsorption energies and the d-band center of the system. The variation of adsorption energy from the one Pd-Au composition to the other can be tentatively assigned to be due to the ligand and coordination effects. Also, the ensemble effects are important; without the right ensemble the adsorption is weak or endothermic. 相似文献
38.
Karoliina Junka Ilari Filpponen Tom Lindström Janne Laine 《Cellulose (London, England)》2013,20(6):2887-2895
Total and surface charge of three different carboxymethylated nanofibrillated/microfibrillated cellulose (NFC/MFC) samples were investigated by using titrimetric methods (conductometric and polyelectrolyte (PE) titrations). Conductometric titration was found to be suitable method for the NFC total charge measurements when the back titration with HCl was applied. Surface charge measurements of NFC/MFC were conducted by using both indirect and direct PE titrations. The direct PE titration was found to be a more suitable method for the surface charge determination of NFC/MFC whereas the indirect PE titration produced too high surface charge values. This is presumably due to kinetically locked polyelectrolyte conformations on the NFC/MFC surfaces or entrapment of residual polymer after adsorption onto the NFC/MFC gel network. Finally, NFC was propargyl-functionalized and the changes in surface and total charge were successfully monitored and compared to those of propargyl-functionalized pulp. A good correlation between the titrimetric methods and elemental analysis was observed. 相似文献
39.
Ruxia Fan Dr. Johanna Hakanpää Karoliina Elfving Dr. Helena Taberman Prof. Markus B. Linder Dr. A. Sesilja Aranko 《Angewandte Chemie (International ed. in English)》2023,62(11):e202216371
A type of protein/peptide pair known as Catcher/Tag pair spontaneously forms an intermolecular isopeptide bond which can be applied for biomolecular click reactions. Covalent protein conjugation using Catcher/Tag pairs has turned out to be a valuable tool in biotechnology and biomedicines, but it is essential to increase the current toolbox of orthogonal Catcher/Tag pairs to expand the range of applications further, for example, for controlled multiple-fragment ligation. We report here the engineering of novel Catcher/Tag pairs for protein ligation, aided by a crystal structure of a minimal CnaB domain from Lactobacillus plantarum. We show that a newly engineered pair, called SilkCatcher/Tag enables efficient pH-inducible protein ligation in addition to being compatible with the widely used SpyCatcher/Tag pair. Finally, we demonstrate the use of the SilkCatcher/Tag pair in the production of native-sized highly repetitive spider-silk-like proteins with >90 % purity, which is not possible by traditional recombinant production methods. 相似文献