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51.
52.
Ramzi Zarrougui Mahmoud Dhahbi Daniel Lemordant 《Journal of solution chemistry》2010,39(10):1531-1548
The densities of binary mixtures of ethylammonium nitrate (EAN) ionic liquid (IL) and γ-butyrolactone (BL) have been measured over the entire range of concentrations at 293.15, 298.15, 303.15, 308.15, 313.15 and
318.15 K and under ambient pressure. Experimental densities were used to calculate excess molar volumes VmEV_{m}^{\mathrm{E}}, isobaric and excess isobaric expansion coefficients α and α
E. The excess molar volumes have both negative and positive values, while the excess isobaric expansion coefficients are negative
over the entire composition range. The VmEV_{m}^{\mathrm{E}} values have been fitted to the Redlich-Kister polynomial equation, and other volumetric properties such as the partial molar
volumes V
mi
, the excess partial molar volume VEmiV^{\mathrm{E}}_{mi} and the partial molar volumes at infinite dilution V¥miV^{\infty}_{mi} were calculated. The results have been interpreted in terms of dipole-dipole interactions, hydrogen bonds formation and structural
factors of these mixtures. The FT-Raman spectroscopy study of the intensity variations of some characteristic bands such as
the C=O stretching band at 1763 cm−1, C–O symmetric stretching band at 932 cm−1 and C–C stretching band at 872 cm−1 of BL has been undertaken. The solvation phenomenon is evidenced by the modifications of these band intensities due to the
presence of the IL ions. Moreover, the Raman spectroscopy corroborates the volumetric study. The average number of BL molecules
in the primary solvation shell of the ethylammonium cation lies between 3 and 4 depending on the temperature. 相似文献
53.
The mechanism of the fluoride-free, palladium-catalyzed cross-coupling reaction of potassium (E)-heptenyldimethylsilanolate, K(+)(E)-1(-), with 2-iodothiophene has been investigated through kinetic analysis. The order of each component was determined by plotting the initial rates of the reaction against concentration. These data provided a mechanistic picture which involves a fast and irreversible oxidative insertion of palladium into the aryl iodide and a subsequent intramolecular transmetalation step from a complex containing a silicon-oxygen-palladium linkage. First-order behavior at low concentrations of silanolate with excess palladium(0) complex supports the formation of this complex as the turnover-limiting step. The change to zeroth-order dependence on silanolate at high concentrations is consistent with the intramolecular transmetalation becoming the turnover-limiting step. 相似文献
54.
Barry J. Bauer Aissa Ramzi Da‐Wei Liu Rolf L. Scherrenberg Peter Froehling Jacques Joosten 《Journal of Polymer Science.Polymer Physics》2000,38(1):95-100
Blends were made by solution and melt‐mixing fatty‐acid‐modified dendrimers with various polyolefins. Small‐angle neutron scattering (SANS) was used to determine the miscibility of the blends. Poly(propylene imine) (PPI) dendrimers G1, G3, and G5 [DAB‐dendr‐(NH2)y] with y = 4, 16, and 64, were reacted with stearic acid or stearic acid‐d35 forming amide bonds. The modified dendrimers were then blended with high‐density polyethylene (HDPE), high‐density polyethylene‐d4 (HDPE‐d4), low‐density polyethylene (LDPE), amorphous polypropylene (PP), or an ethylene–butylene copolymer (E‐co‐B). Limiting power law behavior shows that all of the blends are immiscible. It is likely that the dendrimers form a second phase, being finely dispersed, but thermodynamically immiscible. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 95–100, 2000 相似文献
55.
The mechanisms of how dyes and catalysts for solar-driven transformations such as water oxidation to form O2 work have been intensively investigated, however little is known about how their independent photophysical and chemical processes work together. The level of coordination between the dye and the catalyst in time determines the overall water oxidation system''s efficiency. In this computational stochastic kinetics study, we have examined coordination and timing for a Ru-based dye-catalyst diad, [P2Ru(4-mebpy-4′-bimpy)Ru(tpy)(OH2)]4+, where P2 is 4,4′-bisphosphonato-2,2′-bipyridine, 4-mebpy-4′-bimpy is 4-(methylbipyridin-4′-yl)-N-benzimid-N′-pyridine, a bridging ligand, and tpy is (2,2′:6′,2′′-terpyridine), taking advantage of the extensive data available for both dye and catalyst, and direct studies of the diads bound to a semiconductor surface. The simulation results for both ensembles of diads and single diads show that progress through the generally accepted water oxidation catalytic cycle is not controlled by the relatively low flux of solar irradiation or by charge or excitation losses, rather is gated by buildup of intermediates whose chemical reactions are not accelerated by photoexcitations. The stochastics of these thermal reactions govern the level of coordination between the dye and the catalyst. This suggests that catalytic efficiency can be improved in these multiphoton catalytic cycles by providing a means for photostimulation of all intermediates so that the catalytic rate is governed by charge injection under solar illumination alone.Excitations and reactions in a dye−catalyst dyad for solar-driven water oxidation have timing mismatches caused by the stochastics of some catalytic steps. Rather than being perfectly meshed, these processes are like gears with missing teeth. 相似文献
56.
Semigroup Forum - We investigate the structure of the multiplicative semigroup generated by the set of matrices that are unitarily equivalent to a given invertible matrix A. In particular, we give... 相似文献
57.
Bonačić-Koutecký V Kulesza A Gell L Mitrić R Antoine R Bertorelle F Hamouda R Rayane D Broyer M Tabarin T Dugourd P 《Physical chemistry chemical physics : PCCP》2012,14(26):9282-9290
We focus on the functional role of small silver clusters in model hybrid systems involving peptides in the context of a new generation of nanostructured materials for biosensing. The optical properties of hybrids in the gas phase and at support will be addressed with the aim to bridge fundamental and application aspects. We show that extension and enhancement of absorption of peptides can be achieved by small silver clusters due to the interaction of intense intracluster excitations with the π-π* excitations of chromophoric aminoacids. Moreover, we demonstrate that the binding of a peptide to a supported silver cluster can be detected by the optical fingerprint. This illustrates that supported silver clusters can serve as building blocks for biosensing materials. Moreover, the clusters can be used simultaneously to immobilize biomolecules and to increase the sensitivity of detection, thus replacing the standard use of organic dyes and providing label-free detection. Complementary to that, we show that protected silver clusters containing a cluster core and a shell liganded by thiolates exhibit absorption properties with intense transitions in the visible regime which are also suitable for biosensing applications. 相似文献
58.
MR Eskildsen AB Abrahamsen PL Gammel DJ Bishop NH Andersen K Mortensen PC Canfield 《Pramana》2002,58(5-6):903-905
We compare the results of small angle neutron scattering on the flux line lattice (FLL) obtained in the borocarbide superconductor
LuNi2B2C with the applied field along the c- and a-axes. For H‖c the temperature dependence of the FLL structural phase transition from square to hexagonal symmetry was investigated. Above
10 K the transition onset field. H
2(T), rises sharply, bending away from H
c2(T) in contradiction to theoretical predictions of the two merging. For H‖a a first order FLL reorientation transition is observed at H
tr=3–3.5 kOe. Below H
tr the FLL nearest neighbor direction is parallel to the b-axis, and above H
tr to the c-axis. This transition cannot be explained using nonlocal corrections to the London model. 相似文献
59.
Dr. Fredj Ben Bdira Dr. Christopher A. Waudby Dr. Alexander N. Volkov Dr. Sybrin P. Schröder Dr. Eiso AB Prof. Dr. Jeroen D. C. Codée Prof. Dr. Hermen S. Overkleeft Prof. Dr. Johannes M. F. G. Aerts Dr. Hugo van Ingen Prof. Dr. Marcellus Ubbink 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20689-20695
The single-domain GH11 glycosidase from Bacillus circulans (BCX) is involved in the degradation of hemicellulose, which is one of the most abundant renewable biomaterials in nature. We demonstrate that BCX in solution undergoes minimal structural changes during turnover. NMR spectroscopy results show that the rigid protein matrix provides a frame for fast substrate binding in multiple conformations, accompanied by slow conversion, which is attributed to an enzyme-induced substrate distortion. A model is proposed in which the rigid enzyme takes advantage of substrate flexibility to induce a conformation that facilitates the acyl formation step of the hydrolysis reaction. 相似文献
60.
Th. Abdel‐Moghny S. M. Desouky M. Ramzi 《Journal of Dispersion Science and Technology》2013,34(3):397-405
This work pertains to study the asphaltenes aggregates' settling behavior of crude oil in absence and presence of oil‐soluble surfactants including long‐chain fatty acid in the form of amidation and estrification. First, the onset points as a function of light absorbed asphaltenes aggregates were quantified before and after adding asphaltenes dispersants using ultra violet spectroscopy, and the photograph fractal‐like aggregate structures were quantified using Carl Zeiss Trinocular microscope. Second the shear rates against shear stress induced aggregation were also measured in absence and presence of different concentrations of asphaltenes dispersants using Brookfield digital rheometer model LVDV‐III+. The results reviled that the asphaltenes aggregates are found to depend on toluene–heptane ratios. In absence of dispersant the accumulated and aggregates clusters of asphaltenes are formed at heptane: toluene ratio of 50∶50. Whereas, in the presence of dispersant the asphaltenes are solvated at heptane: toluene ratio of 60∶40, followed by appearance of stronger and dots aggregates clusters at a ratio of 70∶30, and finally, a larger aggregates growing at heptane: toluene ratio of 80∶20. The dispersant solvates the asphaltenes and maintains them in solution, while their surface activity remains high. This means that the dispersant apparently functioned well in decreasing the degree of flocculation and precipitation beyond the critical micelle concentration (CMC) of asphaltenes at 0.0027 g/L. Also, the reduction in the viscosity in presence of dispersant suggests that the asphaltenes aggregates are highly porous and very fragile. 相似文献