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21.
DFT calculations have been carried out for 2-, 3- and 4-methoxybenzyl alcohol radical cations (1+, 3+ and 4+, respectively) and the α-methyl derivatives 2+ and 5+ using the UB3LYP/6-31G(d) method. The theoretical results have been compared with the experimental rate constants for deprotonation of 1+-5+ under acidic and basic conditions. In acidic solution, the decay of 1+-5+ proceeds by cleavage of the C-H bond, while in the presence of −OH all the radical cations undergo deprotonation from the α-OH group. This pH-dependent change in mechanism has been interpreted qualitatively in terms of simple frontier molecular orbital theory. The −OH induced α-O-H deprotonation is consistent with a charge controlled reaction, whereas the C-H deprotonation, observed when the base is H2O, appears to be affected by frontier orbital interactions. 相似文献
22.
Irene Carpani Mario Berrettoni Massimo Gazzano 《Journal of solid state chemistry》2006,179(12):3981-3988
A Ni, Al hydrotalcite-like compound (Htlc) has been proven an useful host material for an alternative synthesis of a K+-free mixed hexacyanoferrate Ni1.5FeIII(CN)6, which is very difficult to obtain in bulk. The first stage of the procedure consists in the intercalation of hexacyanoferrate(III) inside the Htlc structure. The intercalated Htlc has been treated with a NiNO3 solution. The obtained material has been characterized by XRD, XAS Raman and FT-IR spectroscopy. The voltammetric response of the compound obtained after the complete solubilization of the Htlc host shows a typical fingerprint of nickel hexacyanoferrate material with a very low level of potassium. Elemental analysis confirmed the absence of K+ and thus the occurrence of K+-free nickel hexacyanoferrate (14% yield). 相似文献
23.
Ford S Hofmann M Morley CP Roberts JL Di Vaira M 《Organic & biomolecular chemistry》2005,3(21):3990-3995
Bis(1,2,3,4-tetramethylcyclopentadienyl)selane (1) has been prepared by the reaction of tetramethylcyclopentadienyllithium (Cp(t)Li) with selenium bis(diethyldithiocarbamate). Treatment of Cp(t)Li with elemental selenium, followed by air oxidation, led to loss of the allylic hydrogen atom, and formation of the novel tricyclic compound 1,4,5,6,7,10,11,12-octamethyltricyclo[7.3.0.0]-2,8-diselenadodeca-3,5,9,11-tetraene (2). The sulfur analogue of 2 has been obtained by a similar procedure. The X-ray crystal structures of compounds 1 and 2 have been determined, and the molecular geometry observed for has been probed using DFT calculations. 相似文献
24.
Garavelli M Ruggeri F Ogliaro F Bearpark MJ Bernardi F Olivucci M Robb MA 《Journal of computational chemistry》2003,24(11):1357-1363
MMVB is a QM/MM hybrid method, consisting of a molecular mechanics force field coupled to a valence bond Heisenberg Hamiltonian parametrized from ab initio CASSCF calculations on several prototype molecules. The Heisenberg Hamiltonian matrix elements Q(ij) and K(ij), whose expressions are partitioned here into a primary contribution and second-order correction terms, are calculated analytically in MMVB. When the original MMVB force field fails to produce potential energy surfaces accurate enough for dynamics calculations, we show that significant improvements can be made by refitting the second-order correction terms for the particular molecule(s) being studied. This "local" reparametrization is based on values of K(ij) extracted (using effective Hamiltonian techniques) from CASSCF calculations on the same molecule(s). The method is demonstrated for the photoisomerization of s-cis butadiene, and we explain how the correction terms that enabled a successful MMVB dynamics study [Garavelli, M.; Bernardi, F.; Olivucci, M.; Bearpark, M. J.; Klein, S.; Robb, M. A. J Phys Chem A 2001, 105, 11496] were refitted. 相似文献
25.
Carlos Rodríguez-Abreu Massimo Lazzari Dharmesh Varade Masaya Kaneko Kenji Aramaki Manuel Arturo López Quintela 《Colloid and polymer science》2007,285(6):673-680
The structure and rheological properties of a poly(dimethylsiloxane)-graft-poly(oxyethylene) copolymer at high concentrations
in block-selective solvents were studied by small-angle X-ray scattering (SAXS) and rheometry. Analysis of SAXS data indicates
that quasispherical, reverse micellar aggregates (with no ordered packing) are present in concentrated solutions of the copolymer
in nonpolar solvents, and that upon addition of water, the size of such aggregates increases due to the solubilization inside
the micellar cores. The viscosity of concentrated polymer solutions increases exponentially as water is added, and finally,
viscoelastic, gel-like behavior is found in the vicinity of the phase separation limit. It was found that small silver nanoparticles
with an average diameter of ≈3 nm can be synthesized inside the copolymer aggregates without the need of a reducing agent;
namely, particles embedded in a viscoelastic matrix are obtained. The synthesis seems to follow first-order kinetics.
Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users. 相似文献
26.
Bruno P Caselli M de Gennaro G De Rienzo M Ielpo P Manigrassi D 《Annali di chimica》2002,92(9):815-824
In this paper an application of new procedures for atmospheric particulate analysis is illustrated. PM10, PAHs (benzo[a]anthracene (BaA), benzo[b]fluoranthene (BbF), benzo[j]fluoranthene (BjF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1, 2, 3-cd]pyrene (Ip), dibenzo[a, h]anthracene (DbA)) and heavy metals (Cu, Ni, Zn, Co, Mn, Cd, Fe and Pb) were investigated. PM10 determination was performed by gravimetric method, PAHs were measured by GC-MS, and heavy metals by HPIC. An air quality monitoring campaign on the territory of Bari municipality has been organised, and its results are shown. 相似文献
27.
Pietro Borgna Massimo Pregnolato Anna Gamba Invernizzi Giorgio Mellerio 《Journal of heterocyclic chemistry》1993,30(4):1079-1084
3H-1,2-Dithiolo[3,4-b]pyridine-3-thione ( 10 ) reacts with primary alkylamines to give 1,2-dihydro-2-thioxo-3-pyridinecarbothioamides 11a-g and two minor products. Isothiazolo[5,4-b]pyridine-3(2H)-thiones 12a-g and 3-imino-3H-1,2-dithiolo[3,4-b]pyridines 13a-g were isolated and characterized. Further investigations allowed the synthesis of 12 and 13 in good yield. 相似文献
28.
[reaction: see text] Ytterbium triflate was shown to be an effective catalyst in promoting the synthesis of either isopropyl esters or free alpha-hydroxy-arylacetic acids from substituted aromatic glyoxals and aryl methyl ketones, respectively. The reaction to provide acids starting from differently substituted ketones was carried out by an environmentally friendly method using an aqueous medium as a solvent and giving the adducts in 78-99% yield without any further purification after the usual workup. 相似文献
29.
A new optimization based adaptive control strategy for simulated moving beds (SMBs) is proposed. A linearized reduced order model, which accounts for the periodic nature of the SMB process, is used for online optimization and control. The manipulated variables are the four inlet flow rates, the outputs are the raffinate and extract concentrations. Concentration measurements at the raffinate and extract outlets are used as the feedback information. The state estimate from the periodic Kalman filter is used for the prediction of the outlet concentrations over a chosen horizon. Predicted outlet concentrations are the basis for the calculation of the optimal input adjustments, which maximize the productivity and minimize the desorbent consumption subject to constraints on product purities. The realization of this concept is discussed and the implementation on a virtual eight column SMB platform is assessed, in the case of binary linear systems. For a whole series of typical plant disturbances it is shown that the proposed approach is effective in minimizing off-spec products and in achieving optimal SMB operation, also in the case where there are significant model uncertainties. 相似文献
30.
Polycyclic aromatic hydrocarbons in the atmosphere: monitoring, sources, sinks and fate. II: Sinks and fate 总被引:1,自引:0,他引:1
Vione D Barra S De Gennaro G De Rienzo M Gilardoni S Perrone MG Pozzoli L 《Annali di chimica》2004,94(4):257-268
This paper reviews the transformation processes that polycyclic aromatic hydrocarbons (PAHs) undergo in the atmosphere. These processes can take place both in the gas phase and in the particulate/aerosol one. Among the gas-phase processes, the most important ones are the daytime reaction with *OH and the nighttime reaction with *NO3. The relative importance of the two processes depends on the particular PAH molecule. For instance, gaseous naphthalene is mainly removed from the atmosphere upon reaction with *OH, while gaseous phenanthrene is mainly removed by reaction with *NO3. Oxy-, hydroxy-, and nitro-PAHs are the main transformation intermediates. Reaction with ozone and photolysis play a secondary role in the transformation of gaseous PAHs. The particle-associated processes are usually slower than the gas-phase ones, thus the gas-phase PAHs usually have shorter atmospheric lifetimes than those found on particulate. Due to the higher residence time on particulate when compared with the gas phase, direct or assisted photolysis plays a relevant role in the transformation of particle-associated PAHs. Among the other processes taking place in the condensed phase, nitration plays a very important role due to the health impact of nitro-PAHs, some of them being the most powerful mutagens found so far in atmospheric particulate extracts. 相似文献