Relation between the Catalytic Efficiency of the Synthetic Analogues of Catechol Oxidase with Their Electrochemical Property in the Free State and Substrate-Bound State

2014 ◽  
Vol 53 (16) ◽  
pp. 8257-8269 ◽  
Author(s):  
Prateeti Chakraborty ◽  
Jaydeep Adhikary ◽  
Bipinbihari Ghosh ◽  
Ria Sanyal ◽  
Shyamal Kumar Chattopadhyay ◽  
...  
2020 ◽  
Vol 49 (32) ◽  
pp. 11268-11281 ◽  
Author(s):  
Sabarni Dutta ◽  
Pradip Bhunia ◽  
Júlia Mayans ◽  
Michael G. B. Drew ◽  
Ashutosh Ghosh

Catalytic efficiency of heterometallic Cu(ii)–Mn(ii) complexes towards oxidation of 3,5-DTBC to 3,5-DTBQ is dependent on the basicity and steric requirement of anionic co-ligands.


For some years astrophysicists have been looking for an adequate theory of continuous—as opposed to line—absorption. The natural and generally accepted mechanism is the transition of an electron from a bound state to a free state, or from one free state in the neighbourhood of an ion to another free state of greater energy. The theory hitherto used is KRAMERS’ theory of the converse process of emission by a free electron passing a positive nucleus. Since emission and absorption are intimately connected by thermodynamics, the absorption coefficient can be calculated from KRAMERS’ formulae. Unfortunately, although KRAMERS’ work is in good agreement with laboratory observations of X-rays, it gives an absorption coefficient many times smaller than that found from astronomical observations. KRAMERS used classical electromagnetism, and got over the difficulty of the quantisation of negative energies by distributing the classical emission that involved captures somewhat arbitrarily among the various stationary states. It was evidently desirable to do the same work by means of quantum theory, both for the sake of greater rigour, and in the hope of finding a larger absorption. The foundations of such a theory were laid by OPPENHEIMER,|| upon the bed-rock of SCHRODINGER’s equation, in a paper to which this one is much indebted. The matrix-elements involving positive energies present considerable difficulty, and the approximations used by OPPENHEIMER in his paper of 1927 are unsuitable for stellar applications.


2019 ◽  
Vol 20 (19) ◽  
pp. 4850
Author(s):  
Xue ◽  
Liu ◽  
Zheng

Many studies have provided evidence suggesting that caspases not only contribute to the neurodegeneration associated with Alzheimer’s disease (AD) but also play essential roles in promoting the underlying pathology of this disease. Studies regarding the caspase inhibition draw researchers’ attention through time due to its therapeutic value in the treatment of AD. In this work, we apply the “Movable Type” (MT) free energy method, a Monte Carlo sampling method extrapolating the binding free energy by simulating the partition functions for both free-state and bound-state protein and ligand configurations, to the caspase-inhibitor binding affinity study. Two test benchmarks are introduced to examine the robustness and sensitivity of the MT method concerning the caspase inhibition complexing. The first benchmark employs a large-scale test set including more than a hundred active inhibitors binding to caspase-3. The second benchmark includes several smaller test sets studying the relative binding free energy differences for minor structural changes at the caspase-inhibitor interaction interfaces. Calculation results show that the RMS errors for all test sets are below 1.5 kcal/mol compared to the experimental binding affinity values, demonstrating good performance in simulating the caspase-inhibitor complexing. For better understanding the protein-ligand interaction mechanism, we then take a closer look at the global minimum binding modes and free-state ligand conformations to study two pairs of caspase-inhibitor complexes with (1) different caspase targets binding to the same inhibitor, and (2) different polypeptide inhibitors targeting the same caspase target. By comparing the contact maps at the binding site of different complexes, we revealed how small structural changes affect the caspase-inhibitor interaction energies. Overall, this work provides a new free energy approach for studying the caspase inhibition, with structural insight revealed for both free-state and bound-state molecular configurations.


2013 ◽  
Vol 135 (32) ◽  
pp. 11929-11934 ◽  
Author(s):  
Ana-Cristina Sotomayor-Pérez ◽  
Orso Subrini ◽  
Audrey Hessel ◽  
Daniel Ladant ◽  
Alexandre Chenal

2018 ◽  
Vol 74 (7) ◽  
pp. 643-654 ◽  
Author(s):  
Andreas Schmitt ◽  
Florian Hamann ◽  
Piotr Neumann ◽  
Ralf Ficner

The DEAH-box ATPase Prp2 plays a key role in the activation of the spliceosome as it promotes the transition from the Bactto the catalytically active B* spliceosome. Here, four crystal structures of Prp2 are reported: one of the nucleotide-free state and three different structures of the ADP-bound state. The overall conformation of the helicase core, formed by two RecA-like domains, does not differ significantly between the ADP-bound and the nucleotide-free states. However, intrinsic flexibility of Prp2 is observed, varying the position of the C-terminal domains with respect to the RecA domains. Additionally, in one of the structures a unique ADP conformation is found which has not been observed in any other DEAH-box, DEAD-box or NS3/NPH-II helicase.


2014 ◽  
Vol 106 (2) ◽  
pp. 271a
Author(s):  
Ana Cristina Sotomayor Pérez ◽  
Orso Subrini ◽  
Audrey Hessel ◽  
Daniel Ladant ◽  
Alexandre Chenal

2021 ◽  
Vol 34 (04) ◽  
pp. 1413-1419
Author(s):  
Petr M. Kosianov

The problem in question is relevant due to discrepancy between the results of theoretical and known experimental studies of various interactions of ionizing emission photons with substances, in particular, photo effect and Compton scattering of these photons. The study aimed at carrying out specific measurements using a new method of simultaneously determining the ratio of the number of recoil electrons to the number of photoelectrons. Analysis of the results showed that there are significant discrepancies between theoretical calculations and experimental data. New values of simultaneously measured ratios of cross-sections for heavy atoms using a method invented by the author, and old measurements of these ratios for light atoms usingWilson cloud chamber, when compared with theoretical calculations, show that a significant (by one order and more) one-direction discrepancy is seen for X-ray and gamma emissions over a range of energies in question.It is shown that these discrepancies might be attributed to the fact that an atomic electron is in a free state for a while. Compton scattering occurs with a free electron; photo effect involves only bound electrons. Therefore, Compton scattering cross section is proportional to a period of time, during which electron was in a free state, whereas photo effect cross section is proportional to a time period, during which electron was in a bound state. The article materials might be helpful to perform both fundamental, and applied studies on interaction of light quanta with substance including modelling the phenomena under examination.


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