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41.
Ilaria AdamoFabio Benedetti Federico BertiGiorgio Nardin Stefano Norbedo 《Tetrahedron letters》2003,44(51):9095-9097
4-Acyl-1H-1,2,3-triazoles are formed from diethylaluminum azide and α′-(N,N-dibenzylamino)-α,β-unsaturated ketones by [3+2] cycloaddition of azide, followed by 1,5 hydride transfer to the β carbon of the triazoline side chain and fragmentation of the tertiary amino group promoted by coordination of the latter to the Lewis acid. The structure of a triazole product is confirmed by X-ray crystallography. 相似文献
42.
Daniel R. Coulter Ranty H. Liang Salvador Di Stefano Jovan Moacanin Amitava Gupta 《Chemical physics letters》1982,87(6):594-598
Transient emission studies following pulse radiolysis of solid poly(1-vinyl naphthalene) show existence of excited monomers and two excimers. Quenching experiments indicate that excimers are not formed directly by recombination of ions but probably by trapping of migrating monomeric excitation in performed traps whose density is approximately one in 103. 相似文献
43.
Atmospheric bulk deposition of major and trace elements was measured at Venice from November 1995 to October 1997. Collection was carried out using polyethylene bulk passive samplers, samples being collected bi-weekly. In order to highlight the contribution of the atmosphere to water chemistry and particle budgets in the Lagoon of Venice, the geochemical composition (Si, Al, Ca, Mg, K, Na, Mn, Cr, Zn, Pb, Cd, Cu, As) of dissolved and insoluble bulk fractions was determined by AAS + ICP mass spectrometry. Great sample variability was found, with almost two orders of magnitude between maximum and minimum values for several metals. All fluxes in 1995/96 were 30% lower than in 1996/97, ranging from -3% (Ca) to -57% (Li), except for Zn, Cd and As. On the contrary, the solubility of all elements decreased during 1996/97. Partitioning between soluble and insoluble phases shows that Al, Cr, Fe and Si are mainly in the insoluble form, whereas for As, Ca, Cu, Mg, Na, Ni, K, Pb and Zn the dissolved fraction represents 50-90% of total input. The amount of particle load affects partitioning between dissolved and particulate, especially for Al and Pb. Seasonal variability was evident. The lowest pH values (approximately 5.2) were recorded in winter, causing an increase of solubility for all metals except for As, which showed the highest solubility in summer. 相似文献
44.
Accurate computer simulations of the rotational dynamics of linear molecules solvated in He clusters indicate that the large-size (nanodroplet) regime is attained quickly for light rotors (HCN) and slowly for heavy ones (OCS, N2O, and CO2), thus challenging previously reported results. Those results spurred the view that the different behavior of light rotors with respect to heavy ones-including a smaller reduction of inertia upon solvation of the former-would result from the lack of adiabatic following of the He density upon molecular rotation. We have performed computer experiments in which the rotational dynamics of OCS and HCN molecules was simulated using a fictitious inertia appropriate to the other molecule. These experiments indicate that the approach to the nanodroplet regime, as well as the reduction of the molecular inertia upon solvation, is determined by the anistropy of the potential, more than by the molecular weight. Our findings are in agreement with recent infrared and/or microwave experimental data which, however, are not yet totally conclusive by themselves. 相似文献
45.
The rotational dynamics of CO single molecules solvated in small He clusters (CO @ HeN) has been studied using reptation quantum Monte Carlo simulations for cluster sizes up to N = 30. Our results are in good agreement with the rotovibrational features of the infrared spectrum recently determined for this system and provide a deep insight into the relation between the structure of the cluster and its dynamics. Simulations for large N also provide a prediction of the effective moment of inertia of CO in the He nanodroplet regime, which has not been measured so far. 相似文献
46.
This work reports a potentiometric, calorimetric and spectropolarimetric ultraviolet circular dichroism (UV/CD) study of the interaction of l-malic acid with alkaline metals or (poly)ammonium (methylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, spermine, tetraethylenepentamine and pentaethylenehexamine) cations. Stability data (logK, DeltaG(0)) were obtained potentiometrically for the l-malic acid with (poly)ammonium cations systems; calorimetric measurements (25 degrees C) made it possible to obtain DeltaH(0) and TDeltaS(0) values for the complexes formed in the systems under examination. logK values calculated (for the reaction: H(i)A(i+)+H(j)L((j-z))=ALH(r)((i+j-z)), with r=i+j) range between 0.8 and 4.6, i.e., the interactions are from weak to fairly strong while maximum stability for each system is given by the species with the highest z(anion)xz(cation) (z=charge) value. Enthalpy changes associated with reactions H(n)A(n+)+L(2-)=ALH(n)((n-2)) and H(n)A(n+)+HL(-)=ALH(n+1)((n-1)) are always positive and increase progressively with n. The same is valid for T DeltaS(0) values, which indicate that these species are entropically stabilized, as expected for electrostatic interactions. It was verified that the UV/CD signal depends on both ionic medium and ionic strength value; for comparison, we used the l-malic acid signal recorded in tetramethylammonium chloride as baseline background salt (as in potentiometry). UV/CD spectra were recorded for solutions containing both cationic and anionic species. When the cation was a protonated polyamine, CD spectra calculations were performed for most stable ion pairs: the results show remarkable differences in Deltaepsilon (dm(3) mol(-1) cm(-1)) values at 205 nm (which is the l-malate UV/CD lambda(max)) between the chiral ligand and its complex with a polyamine. 相似文献
47.
Formation and stability of proton-mixed ligand complexes have been studied for the systems H(+)-lysine-aspartic acid, H(+)-lysine-succinic acid and H(+)-glycine malonic acid, in aqueous solution at 25 degrees , by potentiometric technique using the (H(+))-glass electrode. For all these systems it has been found that the species ABH(j) (A and B, first and second ligand, respectively; j = 1, 2, ... m + n - 1; m and n are the maximum protonation degrees of the two ligands, respectively) are formed. The stability of these species is discussed with respect to various factors and, in particular, as a function of speciation problems. 相似文献
48.
A convenient route to new 3-quinolinonyl-pyrazoles and isoxazoles is described through cyclization of 3-[(E)-3-(dimethylamino)-2-propenoyl]-4-hydroxy-1-methyl-2(1H)-quinolinone. The phototoxicity as well as the cytotoxic activities of the title compounds are evaluated against leukemia- and adenocarcinoma-derived cell lines in comparison to the normal human keratinocytes. 相似文献
49.
A variety of branched polyethylenes (PE), ranging from semicrystalline linear low density polyethylene to completely amorphous
low density polyethylene and rubbery PE, can be produced from ethylene alone by tandem catalysis using as oligomerization
catalysts the (imino)pyridyl Co(II) complexes NBTCoCl2 (1) ({6-(benzo[b]thiophen-2-yl)-2-(imine)pyridyl)}CoCl2), NETCoCl2 (2) ({6-(4-ethylthiophen-2-yl)-2-(imine)pyridyl)}CoCl2), or NPhCoCl2 (3) ({6-(phenyl)-2-(imine)pyridyl)}CoCl2) and as a copolymerization catalyst [η5-C5Me4)SiMe2(t-BuN)]TiCl2 (4). The catalytic activity of the systems 1/4/MAO, 2/4/MAO, and 3/4/MAO has been evaluated under comparable experimental conditions (T = 30°C, [ethylene] = 0.35 mol/l), varying the molar fraction of the cobalt precursors. A positive comonomer effect was observed
for all the systems investigated. The maximum productivity (4570 kg PE (mol Ti)−1 h−1) was obtained for the benzothiophenyl-substituted cobalt complex. An effective control of the branching in the polymer backbone
was achieved by varying either the oligomerization catalyst or its molar fraction. Completely amorphous materials with T
g as low as-60°C could be obtained.
The text was submitted by the authors in English. 相似文献
50.
Giovannelli Tommaso Liuzzi Giampaolo Lucidi Stefano Rinaldi Francesco 《Computational Optimization and Applications》2022,82(2):293-327
Computational Optimization and Applications - In this paper, mixed-integer nonsmooth constrained optimization problems are considered, where objective/constraint functions are available only as the... 相似文献