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61.
A biased potential molecular dynamics simulation approach, accelerated molecular dynamics (AMD), has been implemented in the framework of ab initio molecular dynamics for the study of chemical reactions. Using two examples, the double proton transfer reaction in formic acid dimer and the hypothetical adiabatic ring opening and subsequent rearrangement reactions in methylenecyclopropane, it is demonstrated that ab initio AMD can be readily employed to efficiently explore the reactive potential energy surface, allowing the prediction of chemical reactions and the identification of metastable states. An adaptive variant of the AMD method is developed, which additionally affords an accurate representation of both the free-energy surface and the mechanism associated with the chemical reaction of interest and can also provide an estimate of the reaction rate. 相似文献
62.
Henig J Mamedov I Fouskova P Tóth É Logothetis NK Angelovski G Mayer HA 《Inorganic chemistry》2011,50(14):6472-6481
A novel class of 1,4,7,10-tetraazacyclododecane-1,4,7-tris(methylenecarboxylic) acid (DO3A)-based lanthanide complexes with relaxometric response to Ca(2+) was synthesized, and their physicochemical properties were investigated. Four macrocyclic ligands containing an alkyl-aminobis(methylenephosphonate) side chain for Ca(2+)-chelation have been studied (alkyl is propyl, butyl, pentyl, and hexyl for L(1), L(2), L(3), and L(4), respectively). Upon addition of Ca(2+), the r(1) relaxivity of their Gd(3+) complexes decreased up to 61% of the initial value for the best compounds GdL(3) and GdL(4). The relaxivity of the complexes was concentration dependent (it decreases with increasing concentration). Diffusion NMR studies on the Y(3+) analogues evidenced the formation of agglomerates at higher concentrations; the aggregation becomes even more important in the presence of Ca(2+). (31)P NMR experiments on EuL(1) and EuL(4) indicated the coordination of a phosphonate to the Ln(3+) for the ligand with a propyl chain, while phosphonate coordination was not observed for the analogue bearing a hexyl linker. Potentiometric titrations yielded protonation constants of the Gd(3+) complexes. log K(H1) values for all complexes lie between 6.12 and 7.11 whereas log K(H2) values are between 4.61 and 5.87. Luminescence emission spectra recorded on the Eu(3+) complexes confirmed the coordination of a phosphonate group to the Ln(3+) center in EuL(1). Luminescence lifetime measurements showed that Ca-induced agglomeration reduces the hydration number which is the main cause for the change in r(1). Variable temperature (17)O NMR experiments evidenced high water exchange rates on GdL(1), GdL(2), and GdL(3) comparable to that of the aqua ion. 相似文献
63.
A novel sensor consisting of nitrogen-doped multi-walled carbon nanotubes was fabricated by means of chemical vapor deposition technique with decomposition of acetonitrile onto oxidized silicon wafer using ferrocene as catalyst. The electrochemical response of carbon nanotubes-based sensor towards oxidation of paracetamol to N-acetyl-p-quinone imine was investigated in phosphate buffer solution (pH 7.0) by means of standard electrochemical techniques. A quasi-reversible response for oxidation of paracetamol was identified on carbon nanotubes-based sensor with detection limit and sensitivity of 0.485 μM and 0.8406 A M?1 cm?2, respectively. It was found that the nitrogen doping in carbon nanotubes enhances the sensor's detection ability. Namely, electrochemical studies performed on film consisting of pristine carbon nanotubes reveal as well quasi-reversible response towards oxidation of paracetamol but nevertheless poorer detection ability and sensitivity (0.950 μM; 0.601 A M?1 cm?2). The findings strongly suggest the application of nitrogen-doped carbon nanotubes in biosensing. 相似文献
64.
Nikos I. Karachalios Athanasios N. Yannacopoulos 《Journal of Differential Equations》2005,217(1):88-123
We study the asymptotic behavior of solutions of discrete nonlinear Schrödinger-type (DNLS) equations. For a conservative system, we consider the global in time solvability and the question of existence of standing wave solutions. Similarities and differences with the continuous counterpart (NLS-partial differential equation) are pointed out. For a dissipative system we prove existence of a global attractor and its stability under finite-dimensional approximations. Similar questions are treated in a weighted phase space. Finally, we propose possible extensions for various types of DNLS equations. 相似文献
65.
Aggelos Vazaios Nikos Hadjichristidis 《Journal of polymer science. Part A, Polymer chemistry》2005,43(5):1038-1048
Anionic polymerization and high‐vacuum techniques were used to prepare a series of well‐defined polyisoprene, polybutadiene, and polystyrene polymacromonomers. The procedure involved (1) the synthesis of styrenic macromonomers in benzene by the selective reaction of the corresponding macroanion with the chlorine of 4‐(chlorodimethylsilyl)styrene (CDMSS) and (2) the in situ anionic polymerization of the macromonomer without previous isolation. The synthesis of the macromonomers [polyisoprene macromonomer: 11 samples, weight‐average molecular weight (Mw) = 1000–18,000; polybutadiene macromonomer: 5 samples, Mw = 2000–4000; and polystyrene macromonomer: 2 samples, Mw = 1300 and 3600] was monitored by size exclusion chromatography with refractive index/ultraviolet detectors. Selectivity studies with CDMSS indicated that polybutadienyllithum had the highest selectivity, and polystryryllithium the lowest. From kinetic studies it was concluded that the polymerization half‐life times were longer but comparable to those of styrene, and they appeared to only slightly depend on the molecular weight of the macromonomer chain (at least for low degrees of polymerization of the polymacromonomer and for Mw < 7000 for the macromonomer side chain). Dependence on the polymerization degree of the polymacromonomer product was also observed. All the prepared polymacromonomers were characterized by size exclusion chromatography with refractive index, ultraviolet and two‐angle laser light scattering detectors, and NMR spectroscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1038–1048, 2005 相似文献
66.
Hermis Iatrou E. Siakali-Kioulafa Nikos Hadjichristidis Jacques Roovers Jimmy Mays 《Journal of Polymer Science.Polymer Physics》1995,33(13):1925-1932
The synthesis of well-defined, nearly monodispersed, 3-miktoarm (from the greek word μlkτós meaning mixed) star copolymer of the A2B type is described. A and B is either polystyrene (PS), polybutadiene (PBd), or polyisoprene (PI). The sequential controlled addition of living anionic B and A chains to methyltrichlorosilane leads to narrow molecular weight distribution miktoarm star copolymers with homogeneous composition. Characterization was carried out by size exclusion chromatography, low-angle laser light scattering, laser differential refractometry, membrane and vapor pressure osmometry, nuclear magnetic resonance and ultraviolet spectroscopy. Analysis of [η], RH and Rv of the A2B and one A2B2 miktoarm copolymers, suggests that a small expansion of the copolymer occurs either in a good solvent for both species or in a Θ solvent for one of them, as compared with the corresponding star homopolymers. This is in contrast to results obtained on linear block copolymers, and is due to the increased occurrence of heterocontacts in the miktoarm starshaped architecture. © 1995 John Wiley & Sons, Inc. 相似文献
67.
Nikos Theodorakopoulos 《Zeitschrift für Physik A Hadrons and Nuclei》1972,254(5):399-407
The effects of adding a local 4-spin term to the nearest neighbor Ising model are studied. The relevant parameter isx, the ratio of the four- to the two-spin interaction strength. We have evaluated the first six terms of the high temperature susceptibility expansion and found them to be consistent with the value 1.75 of the critical exponent γ. The critical exponent α is shown to remain zero to first order inx, provided that the free energy is analytic inx. We also demonstrate the equivalence of the model examined to an elastic spin system with pure two-spin interactions. 相似文献
68.
Zhu K Kopidakis N Neale NR van de Lagemaat J Frank AJ 《The journal of physical chemistry. B》2006,110(50):25174-25180
The dependence of the electron transport and recombination dynamics on the internal surface area of mesoporous nanocrystalline TiO2 films in dye-sensitized solar cells was investigated. The internal surface area was varied by altering the average particle size in the films. The scaling of the photoelectron density and the electron diffusion coefficient at short circuit with internal surface area confirms the results of a recent study (Kopidakis, N.; Neale, N. R.; Zhu, K.; van de Lagemaat, J.; Frank, A. J. Appl. Phys. Lett. 2005, 87, 202106) that transport-limiting traps are located predominately on the surfaces of the particles. The recombination current density was found to increase superlinearly (with an exponent of 1.40 +/- 0.12) with the internal surface area. This result is at odds with the expected linear dependence of the recombination current density on the surface area when only the film thickness is increased. The observed scaling of the recombination current density with surface area is consistent with recombination being transport-limited. Evidence is also presented confirming that photoinjected electrons recombine with redox species in the electrolyte via surface states rather than from the TiO2 conduction band. 相似文献
69.
Engelkamp H Hatzakis NS Hofkens J De Schryver FC Nolte RJ Rowan AE 《Chemical communications (Cambridge, England)》2006,(9):935-940
Single-enzyme studies suggest that dynamic disorder is a general characteristic of enzyme catalysis. 相似文献
70.
Fahad Sultan Salah Hamodeh Yusuke Murayama Kadharbatcha S. Saleem Nikos Logothetis 《Magnetic resonance imaging》2010
Flattened representations are a useful approach to represent the convoluted complex surface of the neocortex of primates and other large-brained mammals. In this study, we compared the flattened representation of neocortical areas obtained from the recently published MRI and histology atlas of the rhesus monkey brain (Saleem KS, Logothetis NK. A combined MRI and histology atlas of the rhesus monkey brain in stereotaxic coordinates. London: Academic; 2007) with other previously published maps. Our results confirm that flat map representations are advantageous due to their ease of use and that current flat maps are well comparable to each other. Some differences arise due to different distinguishing criteria and here too flat maps can help to reveal them. 相似文献