Quantum chemical models and electronic structure of active centers of heterogeneous polymerization of olefins

2000 ◽  
Vol 41 (2) ◽  
pp. 318-328
Author(s):  
I. I. Zakharov
2019 ◽  
Vol 224 ◽  
pp. 03010
Author(s):  
Ludmila Uvarova ◽  
Ekaterina Romanova ◽  
Nikolai Korobov ◽  
Elena Obukhova ◽  
Ekaterina Krasikova

The general structure and the functional universal mechanism of the active centers of the fermentative metal-containing bio-nanocomplexes are discussed on the basis of the quantum-chemical approach using the conception “protein — machine”. The process, proceeding taking place in the active centers structure is the result of their interaction with the substrates. The active centers quantum-chemical models represent the electron distribution among the complex molecular orbitals (MO). The interaction of the central ions with the ligands is carried out by the donor-acceptor mechanism: the ions provide the connection of the vacant orbitals and connection of the vacant orbitals and the ligands — the unshared electron pair. One of the coordination bonds is functional, using for the interaction with substrates. From the quantum-chemical point of view the functional mechanism of the bio-nanocomplexes is universal. In the final, it is reduced to the functional electron accepting and the leaving in the molecular antibonding orbitals of the complex, inducing the active center transitions from one state to another. The electron-conformational transitions, the active centers changes at its functioning, the role of its protein surrounding may be explained on a basis of the conception “protein — machine”. The specific properties of the investigated bio-nanosystems are involved in the using of the internal valuable information, that is the process is a wave and occurs self-correlatively, and may be described by Kolmogorov-Petrovskii-Piskunov mathematical model. It is fair to say that the discussing bio-nanosystems are the natural intellectual tools, which may be used in the nanobiotechnologies and the spheres of its application are wide. It is necessary to conclude that the metal-containing bio-nanocomplexes are the self-organizing, self-congruent, nonlinear, open systems.


2018 ◽  
Vol 7 (3) ◽  
pp. 172-182
Author(s):  
Natalie Sergeevna Panina ◽  
Alisher Talgatovich Talgatov ◽  
Roman Vladimirovich Suezov ◽  
Nicolay Leonidovich Medvedskiy ◽  
Aleksei Vladimirovich Eremin ◽  
...  

This research aims to study the catalytic cycle reactions for homogeneous selective oxidation of thiol RSH groups to RSSR with the participation of coordination compounds for d-element ions-NiII, PdII, Pt II, CuI , CuII. We used the DFT M06, PBE0 / Def2-TZVP methods to build the quantum chemical models of the reactions. We have developed a mechanism for the functioning of the catalytic system in which primary active centers are either binuclear {M(-OH)2M}n+ or polynuclear {M(μ-OH)2M(μ-OH)2M}2+ sites. Catalysts under consideration should retain stable spatial complementarity at all stages of the process. The main interrelated functions of the binuclear catalysts are the spatial approaching of anions RS– in the inner sphere of the bridged coordination compound required for the disulfide (–S–S–) cross-linking and the two-electron redox transfer during the transformation of these anions into disulfide (СH3)2S2


2015 ◽  
Vol 115 (12) ◽  
pp. 5643-5677 ◽  
Author(s):  
Krishnan Raghavachari ◽  
Arjun Saha

2011 ◽  
Vol 134 (7) ◽  
pp. 074105 ◽  
Author(s):  
Csaba Fábri ◽  
Edit Mátyus ◽  
Attila G. Császár

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