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21.
Piotr Kutrowski Dominika Sukowska Renata Pytlowany Roman Dziembaj 《Reaction Kinetics and Catalysis Letters》2004,81(1):3-11
Catalytic performance of Ba(OH)2 and Sr(OH)2 in self-condensation of acetone was examined in the temperature range from 273 to 303 K. A kinetic model of second order with respect to acetone was used for interpretation of the results obtained for the diacetone alcohol formation.This revised version was published online in December 2005 with corrections to the Cover Date. 相似文献
22.
Piotr Kujawa Annie Audibert‐Hayet Joseph Selb Franoise Candau 《Journal of Polymer Science.Polymer Physics》2004,42(9):1640-1655
Multisticker associative polyelectrolytes of acrylamide (≈86 mol %) and sodium 2‐acrylamido‐2‐methylpropanesulfonate (≈12 mol %), hydrophobically modified with N,N‐dihexylacrylamide groups (≈2 mol %), were prepared with a micellar radical polymerization technique. This process led to multiblock polymers in which the length of the hydrophobic blocks could be controlled through variations in the surfactant‐to‐hydrophobe molar ratio, that is, the number of hydrophobes per micelle (NH). The rheological behavior of aqueous solutions of polymers with the same molecular weight and the same composition but with two different hydrophobic block lengths (NH = 7 or 3 monomer units per block) was investigated as a function of the polymer concentration with steady‐flow, creep, and oscillatory experiments. The critical concentration at the onset of the viscosity enhancement decreased as the length of the hydrophobic segments in the polymers increased. Also, an increase in the NH value significantly enhanced the thickening ability of the polymers and affected the structure of the transient network. In the semidilute unentangled regime, the behavior of the polymer with long hydrophobic segments (NH = 7) was studied in detail. The results were well explained by the sticky Rouse theory of associative polymer dynamics. Finally, the viscosity decreased with an increase in the temperature, mainly because of a lowering of the sample relaxation time. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1640–1655, 2004 相似文献
23.
Kowalczyk P Jaroniec M Kaneko K Terzyk AP Gauden PA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10530-10536
In a previous work, we proposed an improvement of the Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in open-ended cylindrical mesopores. In this paper, we report a further extension of this approach to the capillary condensation/evaporation of nitrogen in siliceous spherical cavities. The main idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the variation of the surface tension in spherical mesopores. In addition, the statistical film thickness (the so-called t-curve), which is evaluated accurately on the basis of adsorption isotherms measured for MCM-41 materials, is used instead of the originally proposed t-curve to take into account the excess chemical potential due to the surface forces. It is shown that the aforementioned modifications of the original DBdB theory that was refined by Ravikovitch and Neimark have significant implications for the pore size analysis of cagelike mesoporous silicas. To verify the proposed improvement of the DBdB pore size analysis (IDBdB), two series of FDU-1 samples, which are well-defined cagelike mesoporous materials (composed of siliceous spherical cavities interconnected by short necks), were used for the evaluation of the pore size distributions (PSDs). The correlation between the spinodal condensation point in the spherical pores predicted by the nonlocal density functional theory (NDFT) developed by Ravikovitch and Neimark and that predicted by the IDBdB theory is very good in the whole range of mesopores. This feature is mirrored to the realistic PSD characterized by the bimodal structure of pores computed from the IDBdB theory. As in the case of open-ended cylindrical pores, the improvement of the classical DBdB theory preserves its simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the average pore size by the NDFT and the powder X-ray diffraction method. 相似文献
24.
For most oxide/electrolyte systems potentiometric titration curves measured for different ionic strengths have a Common Intersection Point (CIP) which corresponds to the Point of Zero Charge (PZC). However, there are systems where a CIP exists but the surface charge at this point does not equal zero (PZC CIP). In this paper theoretical analysis of the systems in which the PZC and CIP do not coincide is presented. It is based on the well-known 2-pK surface charging approach and Triple Layer Model (TLM) as well as the Four Layer Model (FLM) of the electric double layer. The appropriate mathematical criterion for CIP existence was applied with detailed derivations, both for TLM and FLM. Having determined in this manner the parameter values, one can draw proper conclusions about the features of oxide/electrolyte adsorption systems, in which PZC and CIP do not coincide. The values of adsorption parameters are found by fitting simultaneously the obtained theoretical expressions to both of the experimental titration isotherms, and to the individual isotherms of electrolyte cation adsorption measured using radiometric methods. 相似文献
25.
While advances in protein design have made possible the construction of protein architectures with nativelike properties and predictable structures and function, there are as of yet no examples of functional, protein-based, solar energy conversion systems. This communication describes the design and characterization of an artificial reaction center (RC) protein that closely resembles the function of the natural photosynthetic RC. The synthetic protein, designed by the protein design program CORE, participates in multiple reduction/oxidation cycles with exogenous acceptors/donors following photoexcitation. The designed metalloprotein, aRC, consists of a tetrahelical bundle functionalized with two bis-histidine bound metal cofactors: a Ru(bpy)2 moiety and a heme group. Two distinct bis-histidine binding sites were engineered for each of these metal centers. Photoexcitation of aRC results in rapid ET from the RuII complex to the heme group (kET >/= 5 x 1010 s-1) yielding a long-lived (70 ns) charge-separated state (CSS), RuIII/FeII. This long-lived CSS participates in subsequent ET reactions with exogenous donors and acceptors in multiple photocycles, thus mimicking the basic function of native photosynthetic RCs. This study illustrates the successful design and construction of a protein-based functional charge separation device using a combination of automated computational protein design and knowledge of the engineering principles of biological electron tunneling extracted from natural electron-transfer systems. To our knowledge, this represents the first example of a functional protein-based artificial reaction center. 相似文献
26.
Piotr Kowalski Marcin Marszałł Ilona Olędzka Wojciech Czarnowski 《Chromatographia》2007,66(5-6):357-361
Two rapid and popular methods—capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC) have been compared
for analysis of cotinine in human urine. Cotinine was analyzed in less than 7 min, with detection limits of 5 and 3.2 ng mL−1 for CE and HPLC, respectively. The performance of the methods was evaluated in terms of sensitivity, specificity, precision,
accuracy, and limits of detection and quantification. Calibration plots were linear in the range 50–4,000 ng mL−1, at least, and mean recoveries were satisfactory for both techniques. The methods were successfully used for quantification
of cotinine in urine. 相似文献
27.
28.
We study arithmetical properties of homotopy groups of thel-adic completion of Quillen'sK-theory space of number field, with a view on the Dwyer-Friedlander comparison map into étaleK-theory. The relation of these groups toK-theory is a complete analogy to the relation of continuous étale cohomology to étale cohomology. We identify the torsion subgroup of the resulting
term with the subgroup of divisible elements inK
2n
(F). We prove that this
term is sent isomorphically into étaleK-theory, giving some further evidence for the Lichtenbaum-Quillen conjectures. 相似文献
29.
The activity of alumina and silica-alumina modified with nickel and/or boron trifluoride etherate in the transformations of o-xylene and -methylnaphthalene in the presence of gaseous hydrogen has been measured. Dependence between the yields of isomerization reaction and the concentration of Brönsted acid centers on the surface of the catalysts investigated was observed. 相似文献
30.
We prove the Cramér theorem forK-invariant Gaussian measures on irreducible symmetric spacesX=G/K withG semisimple noncompact. To do this we use a kind of Abel transform ofK-invariant measures onX.This research is supported by KBN Grant. 相似文献