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991.
Franco L. Molina Dr. Rafael A. Jara-Toro Dr. Jennifer A. Noble Dr. Claude Dedonder-Lardeux Dr. Christophe Jouvet Prof. Gustavo A. Pino 《Chemphyschem》2023,24(1):e202200324
The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O−…H+…−OCO) features a single local minima, with the proton localized on the O− group (OH…−OCO). However, the structure with the proton localized on the −OCO group (O−…HOCO) is also observed because it falls within the extremity of the vibrational wavefunction of the OH…−OCO isomer along the PT coordinate. The stability of the corresponding radicals, produced upon photodetachment, is strongly dependent on the position of the proton in the anion: the radicals produced from the OH…−OCO isomer decarboxylate without barrier, while the radicals produced from the O−…HOCO isomer are stable. 相似文献
992.
The formation constants of UO2SO4 (aq), UO2(SO4)2(2-), and UO2(SO4)3(4-) were measured in aqueous solutions from 10 to 75 degrees C by time-resolved laser-induced fluorescence spectroscopy (TRLFS). A constant enthalpy of reaction approach was satisfactorily used to fit the thermodynamic parameters of stepwise complex formation reactions in a 0.1 M Na(+) ionic medium: log 10 K 1(25 degrees C) = 2.45 +/- 0.05, Delta r H1 = 29.1 +/- 4.0 kJ x mol(-1), log10 K2(25 degrees C) = 1.03 +/- 0.04, and Delta r H2 = 16.6 +/- 4.5 kJ x mol(-1). While the enthalpy of the UO2(SO4)2(2-) formation reaction is in good agreement with calorimetric data, that for UO2SO4 (aq) is higher than other values by a few kilojoules per mole. Incomplete knowledge of the speciation may have led to an underestimation of Delta r H1 in previous calorimetric studies. In fact, one of the published calorimetric determinations of Delta r H1 is here supported by the TRLFS results only when reinterpreted with a more correct equilibrium constant value, which shifts the fitted Delta r H1 value up by 9 kJ x mol(-1). UO2(SO 4) 3 (4-) was evidenced in a 3 M Na (+) ionic medium: log10 K3(25 degrees C) = 0.76 +/- 0.20 and Delta r H3 = 11 +/- 8 kJ x mol(-1) were obtained. The fluorescence features of the sulfate complexes were observed to depend on the ionic conditions. Changes in the coordination mode (mono- and bidentate) of the sulfate ligands may explain these observations, in line with recent structural data. 相似文献
993.
Gasnier A Barbe JM Bucher C Denat F Moutet JC Saint-Aman E Terech P Royal G 《Inorganic chemistry》2008,47(6):1862-1864
A polytopic cyclam-bis-terpyridine ligand has been used to accomplish an acid-base-triggered formation of either a mononuclear neutral complex or metallopolymers with Cu(2+) ions. A controlled interconversion between these two forms was achieved through the reversible displacement of a Cu(2+) cation from the macrocycle to the terpyridine units. 相似文献
994.
Bossé E Den Auwer C Berthon C Guilbaud P Grigoriev MS Nikitenko S Le Naour C Cannes C Moisy P 《Inorganic chemistry》2008,47(13):5746-5755
The complexes [MeBu 3N] 2[UCl 6] and [BuMe 2Im] 2[UCl 6] were characterized in the solid state and in solution of [MeBu 3N][Tf 2N], [BuMe 2Im][Tf 2N], and [BuMeIm][Tf 2N] room-temperature ionic liquids using single-crystal XRD, EXAFS, electrochemistry, UV-visible absorption spectroscopy, and NMR. In the solid state and in solution, the existence of hydrogen bonding between the UCl 6 (2-) complex and the ionic liquid cations was revealed by these techniques. The MeBu 3N (+) cation interacts with UCl 6 (2-) via the protons on the alpha-carbon atoms of nitrogen. The protons of the imidazolium ring account for the interaction between the BuMe 2Im (+) cation and the UCl 6 (2-) anion. For the BuMeIm (+) cation the major interaction was confirmed between the most acidic proton on C(2) and the chlorides of UCl 6 (2-). The experimental results also show that the intensity of the interaction between the UCl 6 (2-) anion and the cation varies with the ionic liquid cation in the following order: MeBu 3N (+) approximately BuMe 2Im (+) < BuMeIm (+). 相似文献
995.
Bonnet ML Aronica C Chastanet G Pilet G Luneau D Mathonière C Clérac R Robert V 《Inorganic chemistry》2008,47(3):1127-1133
The reaction of a tridentate Schiff base LH (L-: 1,1,1-trifluoro-7-(dimethylamino)-4-methyl-5-aza-3-hepten-2-onato) with a Ni(II) salt in the presence of azide salt has led to a new alternating end-on (EO)/end-to-end (EE) azido-bridged Ni(II) chain of formula {[Ni2(micro1,1-N3)(micro1,3-N3)(L)2(MeOH)2]}n. Its originality lies in the presence of single EE and EO coordination modes for the azide. It crystallizes in the C2/c space group, a=21.570(7) A, b=10.79(1) A, c=16.154(5) A, beta=120.81(2) degrees, Z=4. The chain can be viewed as {Ni2(N3)(L)2(MeOH)2}+ dimeric units linked to each other in a zigzag pattern by the other azide. Magnetic susceptibility and magnetization measurements have been performed and revealed that the chain can magnetically be depicted as isolated {Ni2(N3)} units exhibiting antiferromagnetic interaction (JAF approximately -37 cm(-1)). Ab initio calculations confirmed the efficient magnetic coupling through the EE bridge and vanishingly small EO {Ni2(micro1,1-N3)} interactions. 相似文献
996.
Hyperbranched polyamidoamine as stabilizer for catalytically active nanoparticles in water 总被引:1,自引:0,他引:1
Marty JD Martinez-Aripe E Mingotaud AF Mingotaud C 《Journal of colloid and interface science》2008,326(1):51-54
Poly(amidoamine) hyperbranched polymers (HYPAM) were successfully used to synthesize platinum nanoparticles of ca. 1.8 nm and to stabilize these particles in water. Furthermore these hyperbranched-stabilized platinum nanoparticles proved to be effective and robust for hydrogenation reaction in water. 相似文献
997.
We study a problem that occurs at the end of a logistic stream in a warehouse and which concerns the timetabling of the sorting slots that are used to accommodate the prepared orders before they are dispatched. We consider a set of orders to be prepared in a certain number of preparation shops over a given time horizon. Each order is associated with the truck that will transport it to the customer. A sorting slot is an accumulation area where processed orders wait to be loaded onto a truck. For a given truck a known number of sorting slots is needed from the time the first order for this truck begins to be prepared, right up until the truck’s scheduled departure time. Since several orders destined for different trucks are processed simultaneously, and since the number of sorting slots is limited, the timetabling of these resources is necessary to ensure that all orders can be processed over the considered time horizon. In this paper we describe the general industrial context of the problem and we formalize it. We state that some particular cases of the problem are polynomially solvable while the general problem is NP-complete. We then propose optimization methods for solving the problem. 相似文献
998.
Raimund Bürger Christophe Chalons Luis M. Villada 《Numerical Methods for Partial Differential Equations》2016,32(4):1109-1136
One‐dimensional models of gravity‐driven sedimentation of polydisperse suspensions with particles that belong to N size classes give rise to systems of N strongly coupled, nonlinear first‐order conservation laws for the local solids volume fractions. As the eigenvalues and eigenvectors of the flux Jacobian have no closed algebraic form, characteristic‐wise numerical schemes for these models become involved. Alternative simple schemes for this model directly utilize the velocity functions and are based on splitting the system of conservation laws into two different first‐order quasi‐linear systems, which are solved successively for each time iteration, namely, the Lagrangian and remap steps (so‐called Lagrangian‐remap [LR] schemes). This approach was advanced in (Bürger, Chalons, and Villada, SIAM J Sci Comput 35 (2013), B1341–B1368) for a multiclass Lighthill–Whitham‐Richards traffic model with nonnegative velocities. By incorporating recent antidiffusive techniques for transport equations a new version of these Lagrangian‐antidiffusive remap (L‐AR) schemes for the polydisperse sedimentation model is constructed. These L‐AR schemes are supported by a partial analysis for N = 1. They are total variation diminishing under a suitable CFL condition and therefore converge to a weak solution. Numerical examples illustrate that these schemes, including a more accurate version based on MUSCL extrapolation, are competitive in accuracy and efficiency with several existing schemes. © 2015 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 32: 1109–1136, 2016 相似文献
999.
1000.