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1.
2.
3-Hydroxy-4-hydroxymethyl pyrrolidin-2-ones, easily prepared from the Baylis–Hillman adduct 1-ethyl-4-methyl-2-hydroxy-3-methylenebutanedioate, are useful intermediates in the synthesis of bioactive compounds. In order to understand the mechanism involved in this reaction, vibrational and Montecarlo molecular mechanics conformational analysis on 1-ethyl-4-methyl-2-hydroxy-3-methylenebutanedioate were carried out, confirming the existence of a low energy intramolecular H-bonded five-member ring. 相似文献
3.
M. Vedani G. Angella Paola Bassani D. Ripamonti A. Tuissi 《Journal of Thermal Analysis and Calorimetry》2007,87(1):277-284
Equal channel angular
pressing (ECAP) was carried out on solution annealed samples of Al–Mg–Si–Zr
and Al–Mg–Si–Zr–Sc alloys to achieve a substantial
grain refinement of the materials. Post ECAP aging was then investigated on
the ultrafine grained alloys by DSC and TEM analyses.
DSC scans
were carried out with heating rates ranging from 5 to 30°C min–1.
Peak identification was performed by the support of literature information
and TEM analyses. Precipitation kinetics revealed to be similar for both alloys
but the Sc-free alloy showed a recrystallization peak at temperatures ranging
from 310 to 340°C, depending on the strain accumulated during ECAP. On
the contrary, the Sc-containing alloy showed a greater grain stability. Analyses
of peak positions and of activation energies as a function of ECAP passes
experienced by the samples revealed large modifications of precipitation kinetics
in the ultrafine-grained alloys with respect to the coarse-grained materials. 相似文献
4.
Valery Agoshkov Paola Gervasio Alfio Quarteroni 《Mediterranean Journal of Mathematics》2006,3(2):147-176
New domain decomposition methods (DDM) based on optimal control approach are introduced for the coupling of first and second
order equations on overlapping subdomains. Several cost functionals and control functions are proposed. Uniqueness and existence
results are proved for the coupled problem, and the convergence of iterative processes is analyzed.
The work was supported by the Russian Foundation for Basic Research (04-01-00615) and it was partly carried out while the
first author was visiting the IACS at EPFL. 相似文献
5.
6.
This paper presents some properties of two restricted classes of multi-degree-of-freedom potential systems subjected to Gaussian white-noise excitations. Specifically, potential systems which exhibit damping terms with energy-dependent polynomial form are referred to. In this context, first systems with coupled stiffness terms and damping terms depending on the total energy are investigated. Then, systems with uncoupled stiffness terms and damping terms depending on the total energy in each degree-of-freedom are considered. For these two classes, it is found that algebraic relations among the stationary statistical moments of the energy functions can be derived by applying standard tools of Itô calculus. Further, it is noted that these relations are very useful within the framework of an equivalent statistical non-linearization technique to build approximate solutions for arbitrary non-linear systems. 相似文献
7.
Laura Montanaro K. Belgacem P. Llewellyn F. Rouquerol F. Merlo Paola Palmero 《Journal of Thermal Analysis and Calorimetry》2007,88(3):789-793
Wet chemical synthesis of precursor oxide ceramics is a method to obtain small particulate powders. Such powders are far more
prone to ageing in air than more traditional precursors. Thermogravimetric analysis is used to highlight the species responsible
for the ageing of ceramic precursors. Indeed water and carbon dioxide are observed to evolve from aged powders. Ceramics obtained
from aged precursors can reach a very low final density with respect to the theoretical value. A large degree of the original
sintering properties can be recovered after washing the aged powders with ethanol in a basic medium. 相似文献
8.
9.
Apparent molal heat capacities
of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry
in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental
values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions
between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of
ΔC
p
for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined. 相似文献
10.
Catellani M Mealli C Motti E Paoli P Perez-Carreño E Pregosin PS 《Journal of the American Chemical Society》2002,124(16):4336-4346
A series of dichloro-bridged arylbicycloheptylpalladium complexes have been synthesized and characterized by means of NMR spectroscopy. The compound [(C16H19)PdCl]2*CH2Cl2 with ortho and para methyl substituents at the arene has been characterized by means of X-ray diffraction techniques. The C(ipso) atom of the arene lies almost at the fourth planar coordination site of the metal [Pd-C(ipso) = 2.22(1) A (average)], and due to the arene's tilting, the substituted C(ortho) atom is relatively close to the metal atom [2.54(1) A (average)]. The coordinated C(ipso)-C(ortho) linkage, in a seemingly dihapto coordination, is anti with respect to the CH2 bridge of the bicycloheptyl unit. Variable-temperature NMR experiments for the para-substituted dimer 9 reveal restricted rotation of the two aryl groups about the corresponding C-C(ipso) bonds (DeltaE < or =17 kcal x mol(-1)). DFT-B3LYP calculations have been carried out on the known and similar monomer (phenylbicycloheptenyl)Pd(PPh3)I (4) and its related substituted derivatives. The essential results are as follows: (i) The potential energy surface for twisting the phenyl ring away from the symmetric eta(1) coordination in 4 is very flat (DeltaE < or = 1 kcal x mol(-1)) whereas an Atoms in Molecules analysis excludes the existence of an actual Pd-C(ortho) bond in the seemingly eta2-type conformer. (ii) Complete rotation of the unsubstituted phenyl ring is not facile but feasible. A significant strain affects the transition-state structure featuring a Pd-HC(aryl) agostic-type bond. The calculated destabilization of 10.3 kcal x mol(-1), with respect to the ground state, can be compared to the experimental barrier of the dimer 9. (iii) Various methyl-substituted derivatives of 4 have been optimized, and their structural and energetic trends are discussed. An almost ideal eta1 coordination is shown by the anti conformer of the C(ortho)-substituted complex due steric effects. For all of the other cases, a slipped eta2 coordination may be described. As a general conclusion, the unsaturated metal center receives pi electron density of the arene mainly through its C(ipso) atom. The effect may be slightly improved if the C(ortho) atom also gets closer to the metal, but in no case, does the slipped eta2 coordination seem to be crucial for the stability of the system. 相似文献