Functionalization methods reactions

Mineva T, Russo N and Sicilia E 1998 Solvation effects on reaction profiles by the polarizable continuum model coupled with Gaussian density functional method J. Oomp. Ohem. 19 290-9... 

In wet-air oxidation, the aqueous mixture is heated under pressure ia the presence of air, which oxidi2es the organic material. The efficiency of the oxidation process is a function of reaction time and temperature. The oxidation products are generally less complex and can be treated by conventional biological methods (31). The reactor usually operates between 177 and 321°C with pressures of 2.52—20.8 MPa (350—3000 psig). 

The use of QM-MD as opposed to QM-MM minimization techniques is computationally intensive and thus precluded the use of an ab initio or density functional method for the quantum region. This study was performed with an AMi Hamiltonian, and the first step of the dephosphorylation reaction was studied (see Fig. 4). Because of the important role that phosphorus has in biological systems [62], phosphatase reactions have been studied extensively [63]. From experimental data it is believed that Cys-i2 and Asp-i29 residues are involved in the first step of the dephosphorylation reaction of BPTP [64,65]. Alaliambra et al. [30] included the side chains of the phosphorylated tyrosine, Cys-i2, and Asp-i 29 in the quantum region, with link atoms used at the quantum/classical boundaries. In this study the protein was not truncated and was surrounded with a 24 A radius sphere of water molecules. Stochastic boundary methods were applied [66]. 

In general, stabilizers function by reaction with proplnt decompn products. A number of methods have been described and a preliminary evaluation of these methods was conducted by several labs under a cooperative program. Based on results from these screening tests, the PicArsn spec tropho tome trie methods for available stabilizer and primary degradation products were selected for further study. The initial phase of this program was an attempt to standardize the necessary spectrophotometric factors. Significant differences with regard to the factors obtained... 

In particular, reactions involving transition-metals have attracted a lot of interest recently because of the connection to catalytic and enzymatic processes. Unfortunately, the proper computational description of such reactions is one of the great challenges of today s theoretical chemistry and the question for the general applicability of density functional methods in the field is an area of active research. We chose to provide a single but - as we think - representative example to illustrate the difficulties one has to face in theoretical studies of transition-metal reactivity. 

Andzelm, J., Sosa, C., Eades, R. A., 1993, Theoretical Study of Chemical Reactions Using Density Functional Methods With Nonlocal Corrections , J. Phys. Chem, 97, 4664. 

The preparation and reactions of metal cluster ions containing three or more different elements is an area with a paucity of results. The metal cyanides of Zn, Cd (258), Cu, and Ag (259) have been subjected to a LA-FT-ICR study and the Cu and Ag complex ions reacted with various reagents (2,256). The [M (CN) ]+ and [M (CN) +11 ions of copper, where n = 1-5, were calculated to be linear using the density functional method. The silver ions were assumed to have similar structures. The anions [M (CN) +1 of both copper and silver were unreactive to a variety of donor molecules but the cations M (CN) H + reacted with various donor molecules. In each case, where reactions took place, the maximum number of ligands added to the cation was three and this only occurred for the reactions of ammonia with [Cu2(CN)]+, [Cu3(CN)2]+, [Ag3(CN)2]+, and [ Ag4(CN)3]+. Most of the ions reacted sequentially with two molecules of the donor with the order of reactivity being Cu > Ag and NH3 > H2S > CO. 

Catalytic reactions of methanol on an Mo(112)-(lX2)-0 surface under a constant flow of CH3OH and 02 (10 6—10 5 Pa) were monitored as a function of reaction time by the temperature-jump method. Total amounts of the products are summarized in Table 8.3. When only CH3OH was fed, the reaction rate exponentially decayed with reaction time. After the reaction ceased in both conditions, the surfaces were covered with nearly 1 ML of C(a) (Table 8.3) and the sharp (1X2) LEED subspots of the surface before the reaction almost disappeared due to an increase in background intensity. As shown in Table 8.3, the selectivity of the reaction at 560 K is similar to that obtained by TPR (Table 8.2). The C(a) species formed with 26% selectivity cover the surface, resulting in the exponential decay of the reaction rate. O(a) species are also formed on the surface but they are desorbed as H20 by reaction with hydrogen atoms. It should be noted that neither C(a) nor a small amount of O(a) change the selectivity in this case. 

The kinetics of PAA, synthesized from 4,4 -oxydianiline and pyromellitic dianhydride, solid-state imidization both in filler absence and with addition of 2 phr Na+-montmorillonite was studied [1], The nanofiller was treated by solution of P-phenylenediamine in HC1 and then washed by de-ionized water to ensure a complete removal of chloride ions. The conversion (imidization) degree Q was determined as a function of reaction duration t with the aid of Fourier transformation of IR-spectra bands 726 and 1014 cm 1. The samples for FTIR study were obtained by spin-coating of PAA/Na+-montmorillonite mixture solution in N,N-dimethylacetamide on KBr disks, which then were dried in vacuum for 48 h at 303 K. It was shown, that the used in paper [1] method gives exfoliated nanocomposites. The other details of nanocomposites polyimid/Na+-montmorillonite synthesis and study in paper [1] were adduced. The solid-state imidization process was made at four temperatures 7) 423, 473, 503 and 523 K. 

The reaction pathways of conjugate addition of Me2CuLi and Me2CuLi LiCl have been studied for acrolein [79] and cydohexenone [80] with the aid of density functional methods, and fit favorably with the NMR properties of intermediates, kinetic isotope effects [81], and the diastereofacial selectivity. A similar mechanism also operates in this reaction, as summarized in Scheme 10.5. The rate-determining step of the reaction (TScc) is the C-C bond formation caused by reductive elimination from Cu " to give Cu. ... 

When the electrode reaction (2.30) is electrochemically reversible, (2.37) and (2.38) are combined with the Nemst equation (1.8) yielding an integral eqnation that relates the current with time and the electrode potential. The nnmerical solntion derived by the step function method [52] is given by the following recursive formulae ... 

The physical meaning of condition (2.233) is that the diffusion of the electroactive species is blocked at the distance x = Z, i.e., where L is the thickness of the film. This bormdary condition complicates significantly the mathematical procedure compared to the semi-infinite diffusion case. To resolve the mathematical complexity, recently a novel mathematical approach has been developed which is based on the modification of the step function method [162], as elaborated in more detail in the Appendix. The numerical solution for a reversible electrode reaction is given by [155] ... 

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